Methods for depositing fluorine/carbon-free conformal tungsten

Method of depositing fluorine-free/carbon conformal tungsten

METHODS FOR DEPOSITING FLUORINE/CARBON-FREE CONFORMAL TUNGSTEN

The embodiments of the present invention are related to the processing of semiconductor substrates. More specifically, the embodiment of the present invention relates to a method for low-temperature deposition of a tungsten layer or a tungsten silicide layer on a semiconductor substrate using atomic layer deposition technology.

The semiconductor processing industry continues to seek greater throughput while increasing the uniformity of layers deposited on substrates with larger surface areas. The combination of these same factors and new materials also provides higher integration of circuits per unit area of the substrate. As circuit integration increases, the need for greater uniformity of layer thickness and process control increases. Therefore, various techniques have been developed to deposit layers on substrates in a cost-effective manner while maintaining control over the characteristics of the layers.

Chemical vapor deposition (CVD) is one of the most common deposition processes used to deposit layers on substrates. CVD is a flux-related deposition technique, which requires precise control of the substrate temperature and precursors introduced into the processing chamber to produce a desired layer of uniform thickness. These requirements become more important as the size of the substrate increases, which requires more complicated chamber design and gas flow technology to maintain sufficient uniformity.

A variant of CVD that exhibits excellent step coverage is cyclic deposition or atomic layer deposition (ALD). Cyclic deposition is based on atomic layer epitaxy (ALE) and uses chemical adsorption technology to transport precursor molecules on the substrate surface in a continuous cycle. The surface of the substrate is exposed to the first precursor, the purge gas, the second precursor, and the purge gas cyclically. The first precursor and the second precursor react to form a product compound as a thin film on the surface of the substrate. This cycle is repeated to form a layer with the desired thickness.

A thin film layer is formed at a high deposition rate while providing sufficient step coverage for conflicting characteristics, and these conflicting characteristics often require sacrificing one of them to obtain the other. This conflict is especially obvious when the refractory metal layer is deposited on the gap or the through hole during the contact between adjacent metal layers separated by the dielectric layer to form the interconnection. Historically, CVD technology has been used to deposit conductive materials such as refractory metals to form contacts economically and quickly. Due to the increasing integration of semiconductor circuit systems, tungsten has been used based on excellent step coverage. Therefore, the use of CVD technology to deposit tungsten enjoys a wide range of applications in semiconductor processing due to the high throughput of the process.

However, the deposition of tungsten by the conventional CVD method is accompanied by several disadvantages. For example, the ALD process deposits a thin film of tungsten into a through hole with a high aspect ratio (for example, 20), while the conventional CVD process usually results in a "staggered fracture" similar to the through hole and is not completely filled. Similarly, blanket deposition of a tungsten layer on a semiconductor wafer is very time-consuming at temperatures below 400°C. The deposition rate of tungsten can be increased by increasing the deposition temperature to, for example, about 500°C to about 550°C. However, the temperature in this higher range may damage the structural and operational integrity of the lower part of the integrated circuit being formed. The use of tungsten also affects the photolithography step during the manufacturing process. Frustration, because the use of tungsten results in a relatively rough surface (related to thickness and wavelength) with a reflectance of 70% or less than that of silicon. In addition, tungsten has proven difficult to deposit uniformly. Poor surface uniformity usually increases the sheet resistivity.

In high-k metal gates with alternative gate solutions, when the technology node reaches 20nm and below, the feature structure that needs to be filled becomes extremely small. It is necessary to well control the shape retention of the work function film and the properties of the film (no harmful elements including fluorine). In addition, when thin film stacks are developed for smaller feature structures due to the very limited occupied area inside the smaller structure, it is necessary to combine several functional layers (such as WF layer, nucleation layer) that have been used on larger structures. , Barrier layer).

Tungsten film and tungsten silicide (WSi_x) The film system introduces fluorine mainly based on WF₆The CVD/ALD process cannot be directly deposited on the gate before the barrier layer and nucleation layer are deposited. Tungsten precursors with metal oxide ligands suffer from the disadvantage of high carbon content, while other halide precursors such as chlorides are processed at high temperatures (600°C and more than 600°C) and are not suitable for gate replacement processes. The high temperature CVD process also suffers from the disadvantage of poor step coverage.

The tungsten metal deposition process can be performed by reacting with hydrogen. However, the reaction is strictly limited by the dissociation of hydrogen. Hydrogen plasma can increase the reaction rate but can cause damage to the substrate or the film being formed. Hydrogen radicals can also react with tungsten precursors to form tungsten films. However, the "hot wire" commonly used to generate free radicals is not compatible with tungsten precursors.

Therefore, in this technical field, an improved technique for depositing tungsten layers with good conformal properties using atomic layer deposition techniques is needed.

One or more embodiments of the present invention are directed to processing methods that include sequentially exposing a substrate to a first reaction gas and a second reaction gas containing a tungsten-containing compound to form a tungsten-containing thin film, the tungsten-containing compound Contains empirical W_xCl_5xThe compound.

Some embodiments of the present invention are directed to processing methods. The method includes: positioning a substrate in a processing chamber and sequentially exposing at least a part of the substrate to a first reaction gas and a second reaction gas at a temperature less than or equal to about 475° C. to form a tungsten-containing film, and the first reaction gas Contains tungsten pentachloride, with empirical formula W_xCl_5xOne or more of its compounds or tungsten hexachloride.

Some embodiments of the present invention are directed to depositing WSi_xThin film method. The method includes: positioning a substrate in a processing chamber; and sequentially exposing at least a portion of the substrate to a first reaction gas and a second reaction gas at a temperature less than or equal to about 475°C to form WSi_xfilm. The first reaction gas contains tungsten pentachloride and has an empirical formula W_xCl_5xThe second reaction gas contains silicon-containing gas, and the ratio of silicon-containing gas to tungsten-containing gas is in the range of about 100:2 to about 100:0.2.

Some embodiments of the present invention are directed to processing methods that include sequentially exposing at least a portion of a substrate in a processing chamber to a first reactive gas containing a tungsten compound and a second reactive gas containing hydrogen radicals. Form a tungsten-containing thin film, the tungsten-containing compound has an empirical formula WCl₅Or WCl₆。

One or more embodiments of the present invention are directed to a processing method, the processing method comprising: positioning a substrate in a processing chamber containing a gas distribution assembly, the gas distribution assembly including a plurality of elongated gas ports, the plurality of elongated gas ports The gas port includes a first reactive gas port and a second reactive gas port. Gas port with empirical WCl₅Or WCl₆The first reaction gas containing the tungsten compound is in fluid communication and the second reaction gas port is in fluid communication with the second reaction gas containing hydrogen. The gas distribution component allows both the first reaction gas and the second reaction gas to flow into the processing chamber at the same time. The second reaction gas is passed through the heating element to generate hydrogen radicals in the second reaction gas. At least a part of the substrate is sequentially exposed to hydrogen radicals in the first reaction gas and the second reaction gas to form a tungsten film on the substrate.

In some embodiments, the second reaction gas includes a hydrogen-containing compound and the tungsten-containing film is a tungsten film. In some embodiments, the tungsten-containing film consists essentially of tungsten. In one or more embodiments, the second reaction gas includes a nitrogen-containing compound and the tungsten-containing film includes tungsten nitride. In some embodiments, the second reaction gas includes a silicon-containing compound and the tungsten-containing film includes tungsten silicide (WSi_x)。

In some embodiments, the second reaction gas further includes hydrogen. In one or more embodiments, the second reaction gas includes a mixture of a silicon-containing compound and a nitrogen-containing compound, and the tungsten-containing film includes tungsten silicon nitride (WSi_xN_y)。

In some embodiments, the substrate includes a work function metal. In one or more embodiments, the work function metal includes Ti and/or TiAl. In some embodiments, there is no intervening layer between the work function metal and the thin film consisting essentially of tungsten. In one or more embodiments, there is an intervening layer between the work function metal and the thin film consisting essentially of tungsten, the intervening layer having a thickness of less than about 5 angstroms.

In some embodiments, before depositing the tungsten-containing film, the substrate includes an oxide layer, and the method further includes impregnating the substrate with disilane or a mixture of hydrogen and silane at a partial pressure in the range of about 5 Torr to about 20 Torr.

In some embodiments, the tungsten-containing film grows at a rate in the range of about 0.2 Å/cycle and about 3 Å/cycle.

Some embodiments further include generating hydrogen radicals from hydrogen gas. In one or more embodiments, generating hydrogen radicals from hydrogen includes passing hydrogen gas through a heating element that has a temperature sufficient to generate hydrogen radicals. Some embodiments further include heating the heating element to a temperature sufficient to generate hydrogen radicals. In some embodiments, heating the heating element includes providing current flowing through the heating element. One or more embodiments further include applying dynamic tension to the end of the heating element to prevent the heating element from sagging at a temperature sufficient to generate hydrogen radicals.

In some embodiments, the heating element is contained in a housing that is substantially thermally resistant to expansion. In some embodiments, the housing is attached to the front surface of the gas distribution component so that the second reaction gas flowing from the second reaction gas port flows through the housing and around the heating element. One or more embodiments further include moving the substrate relative to the gas distribution assembly so as to expose each part of the substrate to a gas flow consisting essentially of the first reaction gas and the second reaction gas in sequence.

In some embodiments, the substrate is maintained at a temperature of less than about 475°C. In one or more embodiments, the substrate is maintained at a temperature greater than about 350°C.

One or more embodiments of the present invention are directed to a processing method. The processing method includes impregnating a substrate with silane and sequentially exposing the substrate previously impregnated with silane to a first reactive gas and a second reactive gas to form a tungsten thin film. A reaction gas includes a tungsten-containing compound and hydrogen, and the tungsten-containing compound includes an empirical formula W_xCl_5xThe second reaction gas contains a reducing agent. In some implementation In an example, the first reaction gas contains more hydrogen atoms than tungsten atoms. In one or more embodiments, the first reaction gas includes a tungsten-containing compound and hydrogen in a ratio ranging from about 1:2 to 1:20.

Some embodiments of the present invention are directed to processing methods that include depositing a thickness of tungsten in the transistor as a filling material on the work function material, processing the deposited tungsten film and repeating it to form a desired thickness of tungsten filling, wherein Treating the tungsten thin film includes one or more of the following: (1) sequentially exposing the filling material to titanium tetrachloride and ammonia; (2) immersing the filling material in titanium tetrachloride; and (3) applying the filling material Exposure to hydrogen plasma for a time in the range of about 10 seconds to about 30 seconds. In one or more embodiments, the thickness of the tungsten deposited as the filling material in (a) is in the range of about 10 Å to about 30 Å. In some embodiments, the amount of TiN is less than about ½ of the single layer thickness.

In some embodiments, when the tungsten thin film has a thickness of about 70 Å, the tungsten thin film has a grain size greater than about 60 Å. In one or more embodiments, when the tungsten film has a thickness of about 200 Å, the tungsten film has a resistivity of less than about 30 μΩ·cm.

The method of forming a conformal tungsten film includes: exposing a surface to a first reactive gas containing a tungsten compound for a first time and exposing to a second reactive gas containing hydrogen for a second time to deposit the tungsten thin film. Both the time and the second time are less than about 2 seconds. In some embodiments, the tungsten film is grown at a rate of less than about 1 Å/cycle. In one or more embodiments, the tungsten film is grown at a rate of less than about 0.8 Å/cycle.

Some embodiments of the present invention are directed to integrated circuit transistor devices. The integrated circuit transistor devices include a dielectric layer disposed on a channel, The work function metal on the dielectric layer and the filling layer arranged on the work function layer, wherein the filling layer is basically composed of W.

One or more embodiments are directed to an integrated circuit transistor device. The integrated circuit transistor device includes a dielectric layer disposed on a channel, and a work function layer substantially composed of tungsten on the dielectric layer.

In some embodiments, the work function metal is substantially free of fluorine. In one or more embodiments, the filling layer is substantially free of fluorine.

In some embodiments, there is no intervening layer between the work function metal and the thin film consisting essentially of tungsten. In one or more embodiments, there is an intervening layer between the work function metal and the thin film consisting essentially of tungsten, the intervening layer having a thickness of less than about 5 angstroms.

One or more embodiments are directed to processing methods that include depositing a thickness of tungsten in the transistor as a filling material on the work function material; processing the deposited tungsten thin film; and repeating to form a desired thickness of tungsten filling. Treating the tungsten thin film includes one or more of the following: (1) sequentially exposing the filling material to titanium tetrachloride and ammonia; (2) immersing the filling material in titanium tetrachloride; and (3) applying the filling material Exposure to hydrogen plasma for a time in the range of about 10 seconds to about 30 seconds. In some embodiments, the thickness of the tungsten deposited as the filling material in (a) is in the range of about 10 Å to about 30 Å. In one or more embodiments, the amount of TiN is less than about ½ of the single layer thickness.

<p>100Method</p><p>102Step</p><p>103Step</p><p>104Step</p><p>106Step</p><p>108Step</p><p>110Step</p><p>112Step</p><p>114Step</p><p>116Step</p><p>200Processing chamber</p><p>204Wall</p><p>206Chamber body</p><p>208Open</p><p>210Upper surface</p><p>212Substrate support</p><p>214Substrate receiving surface</p><p>216Lifting board</p><p>218Lift Motor</p><p>220Substrate</p><p>222pin</p><p>224Cleaning Ring</p><p>226Clean the passage</p><p>228Lift Motor</p><p>230Exhaust system</p><p>231Exhaust System</p><p>232Pump channel</p><p>234Internal volume</p><p>240Controller</p><p>242Central Processing Unit</p><p>244Support circuit system</p><p>246Memory</p><p>248Associated control software</p><p>250Gas delivery system</p><p>251Gas panel</p><p>252Air source</p><p>253Air source</p><p>255Air source</p><p>256Conduit</p><p>257Valve</p><p>258Conduit</p><p>259Valve</p><p>261Conduit</p><p>263Joint Point</p><p>265Air source</p><p>267Air source</p><p>269Air source</p><p>270 Chamber cover</p><p>271Exhaust System</p><p>272Bottom surface</p><p>273Conduit</p><p>274Extended Channel</p><p>300System</p><p>301Chamber/input surface</p><p>302 Chamber</p><p>303Isolation valve/output surface</p><p>305Enter</p><p>307input</p><p>309input</p><p>310Gas distribution assembly</p><p>311Port</p><p>313Gas port</p><p>315Open</p><p>317Channel</p><p>318Open</p><p>320Syringe</p><p>321Power feedthrough</p><p>323Power cord</p><p>324Power cord</p><p>325Gas port</p><p>327Installation block</p><p>330Syringe</p><p>335Gas port</p><p>340Syringe</p><p>345Gas port</p><p>350Pumping system/arrow</p><p>355Vacuum port</p><p>360Substrate</p><p>361First surface</p><p>363Partition</p><p>365Shuttle</p><p>366Pedestal</p><p>367Top surface</p><p>368Groove</p><p>370Orbit</p><p>390Radiant heat lamp</p><p>398Arrow</p><p>501Heating element</p><p>600Component</p><p>601Heating element</p><p>605Shell</p><p>606Open the inner area</p><p>610Electrical wire</p><p>611Plane</p><p>613 side</p><p>620end</p><p>622end</p><p>630Vertical axis</p><p>700Component</p><p>701Heating element</p><p>705Shell</p><p>720end</p><p>722end</p><p>Part 730</p><p>800Component</p><p>801Heating element</p><p>900Component</p><p>901Heating element</p><p>905Shell</p><p>920end</p><p>922end</p><p>930Extension</p><p>1000Component</p><p>1001Heating element</p><p>1002Cover</p><p>1006Internal area</p><p>1105Shell</p><p>1123Connect</p><p>1124Connect</p><p>1155Shell</p><p>1156Open the inner area</p><p>1200Component</p><p>1201Heating element</p><p>1205Shell</p><p>1206Open the inner area</p><p>1208Insulation part</p><p>1223Power cord</p><p>1224Power cord</p><p>1500System</p><p>1502 Chamber</p><p>1504 Chamber</p><p>1510Robot</p><p>1512 Chamber</p><p>1514 Chamber</p><p>1516 Chamber</p><p>1518 Chamber</p><p>1522 Chamber</p><p>1524 Chamber</p><p>1530Robot</p><p>1532 Chamber</p><p>1534 Chamber</p><p>1536 Chamber</p><p>1538 Chamber</p><p>1550System</p><p>1552 Chamber</p><p>1554 Chamber</p><p>1556 Chamber</p><p>1560Robot</p><p>1562 Chamber</p><p>1564 Chamber</p><p>1566 Chamber</p><p>1568 Chamber</p><p>1570 Chamber</p><p>1572 Chamber</p><p>1600 Chamber</p><p>1617Rotate</p><p>1620Gas distribution assembly/gas injector assembly</p><p>1621Front surface</p><p>1622Sector/Injector Unit</p><p>1624Outer edge</p><p>1640Base Assembly</p><p>1641Top surface</p><p>1643Bottom surface</p><p>1644 edge</p><p>1660wafer</p><p>1661Top surface</p><p>1662Actuator</p><p>1670Gap</p><p>1680 Chamber</p><p>1684Region</p><p>1690Pillars</p><p>A compound</p><p>A'Reactive gas/Reactive gas port</p><p>B compound</p>

Therefore, the above-mentioned characteristic structure of the present invention can be understood in detail, and the present invention briefly summarized above can be described in more detail with reference to the embodiments. Some embodiments are shown in the attached drawings. However, it should be noted that the attached drawings only illustrate the original The typical embodiment of the invention is therefore not intended to be regarded as a limitation of the scope of the invention, because the invention may allow other equally effective embodiments.

Figure 1 illustrates an exemplary process sequence for forming a tungsten layer using a dual pulse cyclic deposition technique according to an embodiment described herein; Figure 2 illustrates an exemplary ALD processing system; Figure 3 illustrates an exemplary spatial ALD processing system; Fig. 4 shows a base for a spatial ALD processing system; Fig. 5 shows a perspective view of a gas distribution assembly according to one or more embodiments of the present invention; Fig. 6 shows a perspective view of a gas distribution assembly according to one or more embodiments of the present invention Front view of the gas distribution assembly of more embodiments; Figure 7 illustrates a front view of the gas distribution assembly according to one or more embodiments of the present invention; Figure 8 illustrates a front view of the gas distribution assembly according to one or more embodiments of the present invention Example of a perspective view of a wire housing for a gas distribution assembly; Figure 9 illustrates a view of an assembly according to one or more embodiments of the present invention; Figure 10 illustrates a view of one or more embodiments of the present invention Example of a view of a component; Figure 11 illustrates a view of a component according to one or more embodiments of the present invention; Figure 12 illustrates a view of a component according to one or more embodiments of the present invention; Figure 13 The figure illustrates the gas according to one or more embodiments of the present invention A cross-sectional view of a volume distribution component; and FIG. 14 illustrates a cross-sectional view of a gas distribution component according to one or more embodiments of the present invention.

Figure 15A illustrates an exemplary integrated processing platform; Figure 15B illustrates another exemplary integrated processing platform; Figure 16 illustrates a schematic cross-sectional view of a batch processing chamber used in an embodiment of the present invention; and Figure 17 illustrates a schematic diagram of a batch processing chamber used in an embodiment of the present invention.

Embodiments of the present invention provide an improved process for depositing tungsten-containing films. The processes of various embodiments use vapor deposition techniques, such as atomic layer deposition (ALD), to provide tungsten films with significantly improved surface uniformity and production level throughput. In some embodiments, the process allows the deposition of tungsten-containing films on the n-metal surface without barrier layers. In some embodiments, the method advantageously increases productivity and efficiency of processing semiconductor substrates by providing conformal deposition of tungsten-containing films at lower processing temperatures, saving the thermal budget of the device being formed.

As used herein, "substrate surface" refers to any part of a substrate on which thin film processing is performed or a part of the surface of a material formed on the substrate. For example, the surface of the substrate that can be processed depends on the application including: materials such as silicon, silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire; and any other materials such as metals , Metal nitrides, metal alloys and other conductive materials. Barrier layer, metal or metal on the surface of the substrate Nitrides include titanium, titanium nitride, tungsten nitride, tantalum, and tantalum nitride. The surface of the substrate may also include dielectric materials, such as silicon dioxide and carbon-doped silicon oxide. The substrate may have various sizes, such as 200mm or 300mm diameter wafers and rectangular or square panels. In some embodiments, the substrate comprises rigid discrete materials.

As used herein, "atomic layer deposition" or "cyclic deposition" refers to sequentially exposing two or more reactive compounds to deposit a layer of material on the surface of a substrate. As used in this specification and the scope of the accompanying patent application, the terms "reactive compound", "reactive gas", "reactive species", "precursor", "process gas", etc. are used interchangeably to mean The substance of the species that reacts with the substrate surface or the material on the substrate surface in the reaction (for example, chemical adsorption, oxidation, reduction). The substrate or parts of the substrate are sequentially exposed to two or more reactive compounds, which are introduced into the reaction zone of the processing chamber. In the time domain ALD process, the exposure to each reactive compound is separated by a time delay to allow each compound to adhere to and/or react on the substrate surface. In a spatial ALD process, different parts of the substrate surface or materials on the substrate surface are exposed to two or more reactive compounds at the same time, so that any known point on the substrate is substantially not exposed to more than one reactive compound at the same time. As used in the scope of this specification and the accompanying patent application, those familiar with the technology will understand that the term "substantially" used in this respect means that there is a possibility that a small part of the substrate may be exposed at the same time due to diffusion Exposure to multiple reactive gases at the same time is improper.

In one aspect of the time-domain ALD process, the first reaction gas (ie, the first precursor or compound A) is pulsed into the reaction zone, followed by Delay in the first time. Immediately afterwards, the second precursor or compound B is pulsed into the reaction zone, followed by a second delay. During each time delay, a purge gas such as argon is introduced into the processing chamber to purify the reaction zone or otherwise remove any residual reaction compounds or by-products from the reaction zone. Alternatively, the purge gas may flow continuously during the entire deposition process, so that only the purge gas flows during the time delay between the pulses of the reactive compound. Or the reactive compound is pulsed until a desired film or film thickness is formed on the surface of the substrate. In either case, the ALD process of pulsed delivery of compound A, purge gas, compound B, and purge gas is a cycle. The cycle can start with compound A or compound B and continue the cycle in the respective sequence until a film with a desired thickness is reached.

In the aspect of the spatial ALD process, the first reaction gas and the second reaction gas (for example, hydrogen radicals) are simultaneously delivered to the reaction zone but separated by an inert gas curtain and/or a vacuum curtain. The substrate is moved relative to the gas delivery device so as to expose any known point on the substrate to the first reaction gas and the second reaction gas.

Figure 1 depicts a method for forming a tungsten-containing layer on a substrate according to some embodiments of the present invention. The method 100 generally starts at 102, where a substrate having a surface is provided and placed in a processing chamber on which a tungsten-containing layer will be formed. As used herein, "substrate surface" refers to any substrate surface on which a layer can be formed. The surface of the substrate may have one or more features formed in the surface of the substrate, one or more layers formed on the surface of the substrate, and a combination of the one or more features and the one or more layers. combination. The substrate (or the surface of the substrate) can be pre-treated before depositing the tungsten-containing layer, for example, by grinding, etching, reducing, oxidizing, halogenating, hydroxylating, annealing, baking, and the like.

The substrate can be any substrate capable of depositing materials on the substrate, such as a silicon substrate, a III-V compound substrate, a silicon germanium (SiGe) substrate, an epitaxial substrate, silicon-on-insulator (SOI) Substrates, display substrates such as liquid crystal display (LCD), plasma display, electro luminescence (EL) lamp display, solar arrays, solar panels, light emitting diode (LED) substrates, semiconductor wafers Wait. In some embodiments, one or more additional layers may be disposed on the substrate such that a tungsten-containing layer may be at least partially formed on the one or more additional layers. For example, in some embodiments, a layer including metal, nitride, oxide, etc. or a combination of the foregoing may be disposed on the substrate and a tungsten-containing layer may be formed on the layer or layers.

In some embodiments, before starting the cyclic deposition process to form a tungsten-containing layer on the substrate (discussed below at 104), the substrate may be exposed to an optional dipping process 103, as shown by the dashed line at 103. In one or more embodiments, the method of depositing the tungsten-containing layer 104 on the substrate does not require a dipping process. This means that there is essentially no advantage to immersion before depositing the thin film. As used in the scope of this specification and the accompanying patent applications, the term "substantially no advantage" used in this regard means that there is an increase of less than about 10% in the deposition rate or the conformality and conformality of the deposited film There is a difference of less than about 20% in uniformity. Having said that, there are embodiments discussed further below, in which prepreg forms an important part of the overall process. In some embodiments, the immersion process may include heating the substrate to an immersion temperature, and then exposing the substrate to an immersion gas. For example, in some embodiments, the substrate may be heated to a temperature of about 100° C. to about 600° C., or in some embodiments, about 200° C. to about 600° C., or in some embodiments, about 300° C. °C to about 500°C, or in some embodiments Medium is about 350°C to about 420°C, or in some embodiments, about 375°C to about 500°C.

In some embodiments, the impregnation gas may include a reducing gas including hydrogen and/or hydride compounds, such as silane compounds (e.g., silane, disilane, trisilane, tetrasilane, chlorosilane, dichlorosilane, four Chlorosilane, hexachlorodisilane, methyl silane, etc.), borane compounds (for example, borane, diborane, triborane, tetraborane, pentaborane, alkyl borane, etc.), phosphine , Ammonia, amine compounds, hydrogen, derivatives of each of the foregoing, combinations of the foregoing, etc. When the reducing gas is present, the reducing gas is adsorbed to the surface of the substrate and/or reacts with the surface of the substrate to form a treated surface. In some embodiments, the treated surface provides a faster deposition process for overall smoother and more uniform subsequent deposition of layers.

In some embodiments, the substrate is subjected to silane impregnation. Some of these embodiments use silane impregnation that is essentially only silane. As used in this specification and the scope of the accompanying patent application, the term "substantially only silane" used in this regard means that the impregnating fluid is 99% or more silane as the impregnating agent. For example, when the diluent (hydrogen) is not included, an impregnation solution of 5% silane in hydrogen will be regarded as 100% silane.

In some embodiments, the reducing gas contains the following hydrogen/hydride flow ratio: about 40:1 or greater, or in some embodiments, about 100:1 or greater, or in some embodiments, about 500 :1 or greater, or in some embodiments, about 800:1 or greater, or in some embodiments, about 1000:1 or greater. In some embodiments, the hydride compound (eg, diborane) may have a flow rate of about 1 sccm to about 75 sccm, or in some embodiments, about 3 sccm To about 30 sccm, or in some embodiments, from about 5 sccm to about 15 sccm. In some embodiments, the hydride compound may be in a carrier gas (eg, hydrogen, nitrogen, argon, helium, etc.) so that the mixture may have the following flow rates: in the range of about 50 sccm to about 500 sccm, or In some embodiments, about 75 sccm to about 400 sccm, or in some embodiments, about 100 sccm to about 300 sccm. In some embodiments, hydrogen can be provided at a flow rate of about 1 slm to about 20 slm, or in some embodiments, from about 3 slm to about 15 slm, or in some embodiments, from about 5 slm to about 10 slm. The hydrogen/hydride flow ratio can be calculated by dividing the total hydrogen flow by the total hydride flow. The total hydrogen flow includes the sum of all hydrogen sources, including the flow of any hydrogen carrier gas and the flow of any independent hydrogen.

In some embodiments, the reducing gas may be mixed inside the processing/deposition chamber or mixed externally and may come from multiple sources. For example, in some embodiments, the substrate is exposed to a reducing gas, the reducing gas system by combining a reduction or hydride compound and a hydrogen mixture (e.g., H₂Medium 5% B₂H₆) Is formed by the gas flow and the hydrogen gas flow. In another example, in some embodiments, the reduced or hydride compound and hydrogen mixture (e.g., H₂Medium 5% B₂H₆The gas flow of) and the gas flow of hydrogen are combined before entering the chamber. Additional process parameters can be used to facilitate the impregnation process. For example, in some embodiments, the dipping process can be performed while maintaining the pressure in the process chamber at about 1 Torr to about 150 Torr, or in some embodiments, from about 1 Torr to about 100 Torr, or at In some embodiments, from about 10 Torr to about 50 Torr, or in some embodiments, from about 20 Torr to about 40 Torr, or in some embodiments, from about 5 Torr to about 20 Torr. In some embodiments, the dipping process can be performed for the following time Interval: within about 1 second to about 90 seconds, or in some embodiments, less than about 60 seconds, or in some embodiments, less than about 30 seconds, or in some embodiments, less than about 10 seconds.

Next, in step 104, a tungsten-containing layer is formed on the substrate. The tungsten-containing layer can be formed through a cyclic deposition process such as atomic layer deposition (ALD). In some embodiments, forming a tungsten-containing layer through a cyclic deposition process may generally include sequentially exposing the substrate to two or more process gases. In the time domain ALD embodiment, the exposure to each process gas is separated by a time delay/pause to allow the components of the process gas to adhere to and/or react on the substrate surface. Alternatively or in combination, in some embodiments, the purge may be performed before exposing the substrate to the process gas and/or after exposing the substrate to the process gas, where an inert gas system is used to perform the purge. For example, the first process gas can be supplied to the process chamber and then purged with an inert gas. Then, the second process gas can be supplied to the process chamber, and then purified with inert gas. In some embodiments, the inert gas can be continuously provided to the process chamber and the first process gas can be dosed or pulsed into the process chamber, and then the second process gas can be dosed or pulsed to the process. Chamber. In these embodiments, a delay or pause may occur between the dosing of the first process gas and the second process gas to allow the continuous flow of inert gas to purge the process chamber between the dosing of the process gas.

In the spatial ALD embodiment, the exposure to each process gas occurs simultaneously to different parts of the substrate, so that a part of the substrate is exposed to the first reactive gas while different parts of the substrate are exposed to the second reactive gas (if only two are used) Kind of reactive gas). The substrate is moved relative to the gas delivery system in order to Each point on the substrate is sequentially exposed to both the first reaction gas and the second reaction gas. In any of the embodiments described above for both the time domain ALD process and the spatial ALD process, the sequence can be repeated until the desired layer thickness is formed on the substrate surface.

As used herein, "pulse" or "dose" is intended to represent the amount of source gas introduced into the process chamber intermittently or discontinuously. The amount of a particular compound in each pulse can vary over time, depending on the duration of the pulse. The specific process gas may include a single compound or a mixture/combination of two or more compounds, for example, the process gas described below.

The duration of each pulse/dose is variable and can be adjusted to suit, for example, the volumetric capacity of the processing chamber and the volume of the vacuum system coupled to the processing chamber. In addition, the dosage time of the process gas can vary according to the flow rate of the process gas, the temperature of the process gas, the type of control valve, the type of process chamber used, and the ability of the process gas to adsorb components on the substrate surface. The dose time can also vary based on the type of layer being formed and the geometry of the device being formed. The dosage time should be long enough to provide a certain volume of compound that is sufficient to adsorb/chemically adsorb to the substantially entire surface of the substrate and form a layer of process gas components on the entire surface.

The process of forming the tungsten-containing layer in step 104 can be started by exposing the substrate to the first reactive gas. In some embodiments, the first reactive gas includes a tungsten precursor (also referred to as a tungsten-containing gas, etc.) and is exposed to the substrate for a first period of time, as shown at 106. The tungsten precursor may be any suitable tungsten-containing gas, including but not limited to halide-based tungsten precursors or organometal-based tungsten precursors. For example, in some embodiments, the tungsten precursor may include tungsten pentachloride (WCl₅), with empirical WCl₅The compound (e.g., W₂Cl₁₀, W₃Cl₁₅), tungsten hexachloride (WCl₆), with empirical WCl₆The compound (e.g., W₂Cl₁₂), tungsten hexafluoride (WF₆). In one or more embodiments, the tungsten-containing precursor is selected from the group consisting of: tungsten pentachloride, WCl with empirical formula₅The compound and tungsten hexachloride. In some embodiments, the tungsten-containing compound includes an empirical formula W_xCl_5xWherein x is greater than or equal to about 1 and y is greater than or equal to about 5. Without being bound by any particular theory of operation, it is believed that changing anions from fluoride to chloride results in larger ions that restrict diffusion, which results in greater conduction. In some embodiments, the tungsten-containing film is substantially carbon-free. As used in the scope of this specification and the accompanying patent applications, the term "substantially carbon-free" means that less than about 1% or 0.5% or 0.1% of carbon atoms are present in the film.

The tungsten-containing process gas can be supplied in one or more pulses or continuously. The flow rate of the tungsten-containing gas can be any suitable flow rate, including but not limited to the following flow rates: in the range of about 1 sccm to about 5000 sccm, or in the range of about 2 sccm to about 4000 sccm, or in the range of about 3 sccm to about 3000 sccm Within or in the range of about 5 sccm to about 2000 sccm. The tungsten-containing precursor can be provided at any suitable pressure, including but not limited to the following pressures: in the range of about 5 mTorr to about 25 Torr, or in the range of about 100 mTorr to about 20 Torr, or in the range of about 5 Torr to In the range of about 20 Torr, or in the range of about 50 mTorr to about 2000 mTorr, or in the range of about 100 mTorr to about 1000 mTorr, or in the range of about 200 mTorr to about 500 mTorr.

The time period for exposing the substrate to the tungsten-containing gas can be to allow the tungsten precursor Any suitable amount of time necessary to form a sufficient nucleation layer on top of the substrate surface. For example, the process gas can flow into the process chamber for a period of about 0.1 second to about 90 seconds. In some time-domain ALD processes, the tungsten-containing gas is exposed to the surface of the substrate for the following time: in the range of about 0.1 second to about 90 seconds, or in the range of about 0.5 second to about 60 seconds, or in the range of about 1 second. In the range of about 2 seconds to about 30 seconds, or in the range of about 2 seconds to about 25 seconds, or in the range of about 3 seconds to about 20 seconds, or in the range of about 4 seconds to about 15 seconds, or It is in the range of about 5 seconds to about 10 seconds.

In some embodiments, the inert gas may be additionally provided to the process chamber at the same time as the tungsten-containing gas. The inert gas may be mixed with a tungsten-containing gas (for example, as a diluent gas) or exist alone and may be pulsed or have a constant flow rate. In some embodiments, the inert gas system flows into the processing chamber at a constant flow rate in the range of about 1 sccm to about 10000 sccm. The inert gas can be any inert gas, for example, argon, helium, neon, a combination of the foregoing, and the like. In one or more embodiments, the tungsten-containing gas system is mixed with argon before flowing into the process chamber.

The temperature of the substrate during deposition can be controlled, for example, by setting the temperature of the substrate support or susceptor. In some embodiments, the substrate is maintained at the following temperature: in the range of about 300°C to about 475°C, or in the range of about 350°C to about 450°C. In one or more embodiments, the substrate is maintained at a temperature of less than about 475°C, or less than about 450°C, or less than about 425°C, or less than about 400°C, or less than about 375°C.

In addition to the foregoing, additional process parameters can be adjusted while exposing the substrate to a tungsten-containing process gas. For example, in some embodiments, the process chamber The chamber can be maintained at a pressure of about 0.3 Torr to about 90 Torr.

In some embodiments, the low-resistivity film (or the tunable grain size film) is pre-impregnated with silane and ALD The combination of W deposition and deposition. For example, the substrate is immersed in substantially only silane before any ALD cycle (ie, in step 103 of Figure 1). The tungsten-containing precursor co-flows with a relatively low amount of hydrogen during the tungsten exposure step 106. The amount of hydrogen co-flowing with the tungsten-containing precursor is low enough so that there is substantially no CVD deposition. The relatively low flow rate of hydrogen is relative to the amount of hydrogen required for reduction in step 110, not relative to the amount of co-flowing tungsten precursor. For example, hydrogen is co-flowed at about 5 sccm (where the amount of hydrogen here is greater than about 2000 times the amount of reduction). In some embodiments, the first reaction gas containing a tungsten-containing compound and hydrogen has more hydrogen atoms than tungsten atoms. In one or more embodiments, the mixture of the tungsten-containing precursor and hydrogen is in the range of about 1:2 to 1:20. The inventors have surprisingly discovered that the tungsten film deposited by the process of silane dipping and hydrogen co-flow has a higher grain size and lower resistivity than other processes. The 70Å tungsten film deposited by standard processes (ie, no silane pre-impregnation and/or no hydrogen co-flow) has a grain size of 33Å. The grain size of a 70Å tungsten film impregnated with silane and co-flowed with hydrogen is about 70Å. In some embodiments, when the thickness of the tungsten film is about 70 Å, the tungsten film has a grain size greater than or equal to about 60 Å or 65 Å. The 200Å tungsten film deposited by the standard process has a resistivity of about 40μΩcm, while the film deposited by the silane immersion and hydrogen co-flow process has a resistivity of about 20μΩcm. In some embodiments, when the tungsten film has a thickness of about 200 Å, the tungsten film has a resistivity less than or equal to about 20 μΩ cm or 25 μΩ cm.

Next, in step 108, the process chamber (especially in time domain ALD) can be purged with an inert gas. (This operation may not be needed in the space ALD process because there is a gas curtain to separate the reaction gas.) The inert gas can be any inert gas, such as argon, helium, neon, etc. In some embodiments, the inert gas may be the same or may be different from the inert gas provided to the process chamber during the exposure of the substrate to the first process gas at 106. In an embodiment where the inert gas is the same, the purification can be performed by transferring the first process gas to the process chamber and allowing the inert gas to flow through the process chamber, thereby purifying any excess first process gas components or reactions. Process chamber of by-products. In some embodiments, the inert gas can be provided at the same flow rate used in combination with the first process gas described above, or in some embodiments, the flow rate can be increased or decreased. For example, in some embodiments, the inert gas may be provided to the process chamber at a flow rate of about 0 sccm to about 10000 sccm to purify the process chamber. In the space ALD, the purge gas curtain is maintained between the flow of reaction gas and may not need to purge the process chamber. However, in some embodiments, the process chamber can be purged with an inert gas.

The flow of inert gas can facilitate the process chamber to remove any excess first process gas components and/or excess reaction by-products to prevent improper gas phase reaction of the first process gas and the second process gas. For example, the flow of inert gas can remove excess tungsten-containing gas in a self-processed chamber, thereby preventing the reaction between the tungsten precursor and the subsequent reaction gas.

Next, in step 110, the substrate is exposed to the second process gas for a second time period. The second process gas reacts with the tungsten-containing compound on the surface of the substrate to produce a deposited film. The second process gas can have a heavy effect on the resulting tungsten film To influence. For example, when the second process gas is H₂When the tungsten film is deposited, when the second reaction gas is silane or disilane, the tungsten silicide film is deposited.

In some embodiments, the second reaction gas contains hydrogen and the resulting formed film is a tungsten film. Hydrogen can be supplied to the surface of the substrate at a flow rate greater than the concentration of the tungsten-containing gas. In one or more embodiments, H₂The flow rate is greater than about 1 times the flow rate of the tungsten-containing gas, or about 100 times the flow rate of the tungsten-containing gas, or within the range of about 3000 to 5000 times the flow rate of the tungsten-containing gas. In time domain ALD, hydrogen can be supplied for the following time: in the range of about 1 second to about 30 seconds, or in the range of about 5 seconds to about 20 seconds, or in the range of about 10 seconds to about 15 seconds. Within range. Hydrogen can be supplied at the following pressures: in the range of about 1 torr to about 30 torr, or in the range of about 5 torr to about 25 torr, or in the range of about 10 torr to about 20 torr, or up to about 50 torr. The temperature of the substrate can be maintained at any suitable temperature. In one or more embodiments, the substrate is maintained at a temperature of less than about 475° C. or at about the same temperature as the temperature of the substrate during the deposition of the tungsten-containing film.

In some embodiments, the conformal coverage of the characteristic structure is performed in both the pulse delivery step and the purification step using small step times of typically about 1 second to 2 seconds. This time is sufficient for the following: reasonable adsorption of the precursor to the surface of the substrate in the pulse delivery step, and purification of the excess precursor or reducing gas from the gas delivery path and the chamber cavity in the purification step. As used in this specification and the scope of the accompanying patent application, the term "reasonable adsorption" is sufficient for the adsorption of thin film growth. In some embodiments, the tungsten film is grown at a rate of less than or equal to about 0.9 Å/cycle, 0.8 Å/cycle, 0.7 Å/cycle, or 0.6 Å/cycle. A lower growth rate is good for conformal growth, while a higher The growth rate (for example, higher than about 1 Å/cycle) tends to grow non-conformal films. One or more embodiments of the present invention are directed to conformal tungsten thin films.

In some embodiments, the second reactive gas contains hydrogen radicals. Hydrogen radicals can be generated by any suitable means, including exposure of hydrogen to the "hot wire". As used in this specification and the scope of the accompanying patent application, the term "hot wire" means any element that can be heated to a temperature sufficient to generate free radicals in the gas flowing around the element. This is also called a heating element.

Therefore, one or more embodiments of the present invention are directed to a method of processing a substrate or depositing a thin film. At least a part of the substrate is sequentially exposed to the first reaction gas and the second reaction gas containing the metal complex. The metal complex can be any suitable metal complex used in ALD processing, including but not limited to organometallic complexes. In some embodiments, the organometallic complex includes a tungsten-containing compound. The tungsten-containing compounds of some embodiments have the empirical formula WCl₅(E.g. WCl₅, W₂Cl₁₀). In one or more embodiments, the tungsten-containing compound has the empirical formula WCl₆(E.g. WCl₆, W₂Cl₁₂). The second reaction gas may contain hydrogen radicals. The method of some embodiments is a method in a space atomic layer deposition chamber or a method performed by a space atomic layer deposition process. Spatial ALD is particularly effective for depositing tungsten thin films using hydrogen radicals, because the free radical generating devices (eg, hot wires) can be isolated from metal organic precursors, which are often incompatible with the hot wire materials.

The second reaction gas (for example, hydrogen) becomes radicalized when passing through the hot wire or heating element. For example, through the H of the hot tungsten wire₂Can cause H^*. These hydrogen radicals react more easily than ground state hydrogen atoms.

To be effective, the heating element must be heated enough to generate free radicals temperature. The temperature. Heating can occur by, for example, passing sufficient current through the heating element to increase the temperature of the heating element.

Then, at 112, the process chamber can be purged with inert gas. The inert gas can be any inert gas, such as argon, helium, neon, etc. In some embodiments, the inert gas may be the same or may be different from the inert gas provided to the process chamber during the previous process step. In an embodiment where the inert gas is the same, the purification can be performed by transferring the second process gas to the process chamber and allowing the inert gas to flow through the process chamber, thereby purifying any excessive second process gas components or reactions. Process chamber of by-products. In some embodiments, the inert gas may be provided at the same flow rate used in conjunction with the second process gas described above, or in some embodiments, the flow rate may be increased or decreased. For example, in some embodiments, the inert gas may be provided to the process chamber at a flow rate of about 0 sccm to about 10000 sccm to purify the process chamber.

Although the general embodiment of the processing method illustrated in Figure 1 includes only two pulses of reactive gas, it should be understood that this is only exemplary and may require additional pulses of reactive gas. For example, the nitride film of some embodiments can be grown by each of the following: a first pulse containing a precursor gas such as tungsten pentachloride, a second pulse with a reducing agent, followed by purification and use of nitrogen The third pulse of transformation. The pulse may repeat the whole or part of the pulse. For example, all three pulses may be repeated or only two may be repeated. This can be changed for each cycle as needed.

Next, at 114, it is determined whether the tungsten-containing layer reaches a predetermined thickness. If the predetermined thickness is not reached, the method 100 returns to 104 to continue forming the tungsten-containing layer until the predetermined or desired thickness is reached. Once the predetermined thickness has been reached, then The method 100 may end or proceed to 116, where an overall deposition process may be performed to deposit the remaining thickness of the tungsten-containing layer. In some embodiments, the overall deposition process may be a CVD process. After depositing the tungsten-containing layer to the desired thickness, the method 100 is generally over and the substrate can be subjected to any further processing. For example, in some embodiments, a CVD process may be performed to deposit the tungsten-containing layer to a target thickness as a whole. For example, in some embodiments, the tungsten-containing layer can be deposited via the ALD or CVD reaction of a tungsten precursor and hydrogen radicals to form an overall layer thickness of about 10 Å to about 10000 Å, or in some embodiments, From about 10 Å to about 1000 Å, or in some embodiments, from about 500 Å to about 5000 Å.

Although the description has generally referred to the tungsten-containing gas as the first gas, those skilled in the art will understand that this is only illustrative. In some embodiments, the substrate is first exposed to the second reactive gas, and then exposed to the tungsten-containing gas.

In any of the above embodiments, each cycle consisting of exposing the substrate to the first process gas, purging with an inert gas, exposing the substrate to the second process gas, and purging with the inert gas can form a substrate with a thickness of about 0.1 Å to A tungsten-containing layer with a thickness of about 1.5Å. In some embodiments, the thickness grows at the following rate: in the range of about 0.1 Å/cycle to about 5 Å/cycle, or in the range of about 0.2 Å/cycle to about 3 Å/cycle, or about 0.3 Å/cycle To within the range of about 2Å/cycle. The sequence can be repeated until the desired overall thickness of the tungsten-containing layer is reached. For example, in some embodiments, the tungsten-containing layer may include an overall thickness of about 2 Å to about 200 Å, or in some embodiments, an overall thickness of about 50 Å. Therefore, the deposition process may require up to about 2000 cycles to achieve the desired thickness.

In any of the above embodiments, the flow rate and/or duration of each pulse may be the same or may be in the process of forming a specific tungsten-containing layer in the overall cycle required Medium change, thereby promoting the layer to have a uniform composition or a graded composition.

In some embodiments, the substrate surface is pre-conditioned. For example, if the surface of the substrate is oxide, it may be desirable to perform pre-impregnation using hydride or a hydride/hydrogen mixture. The hydride adsorbs and/or reacts with the surface of the substrate to form a conditioned surface to allow the formation of a uniform tungsten-containing layer. In some embodiments, the hydride may include silane (Si_xH_y) Compound (e.g., silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), chlorosilane, dichlorosilane (H₂SiCl₂), etc.), borane (B_xH_y) Compound (for example, diborane (B₂H₆), triborane (B₃H₈), pentaborane (B₅H₉), etc.), phosphine (PH₃), derivatives of the foregoing, combinations of the foregoing, etc. In addition, in some embodiments, the hydride may be diluted in a diluent gas, such as an inert gas, such as argon (Ar), helium (He), nitrogen (N₂), hydrogen (H₂)Wait. For example, in these embodiments, the hydride may be provided in a mixture of about 5% hydride and about 95% diluent gas by volume. In some embodiments, for example, where the hydride includes diborane, the flow rate of the hydride may be about 1 sccm to about 75 sccm.

In an embodiment, the tungsten film can be formed by placing a substrate with a metal layer of 10 Å or thicker (such as ALD TiN, TiSiN, TiAl, PVD Ti, TiN), or if it is by placing a substrate with an oxide To form, the base maintained at a temperature in the range of about 400°C to about 475°C is impregnated with disilane or a mixture of hydrogen and silane at a partial pressure of 5 to 20 torr. Tungsten compounds (e.g. WCl₅Or WCl₆) The argon mixture can be pulsed to the wafer surface under 5 to 20 torr, and then purged with argon (or another inert gas). The argon pressure was increased to about 20 Torr and then the hydrogen pulse delivery was started. Pulse delivery of hydrogen radicals can be carried out at a high flow rate to facilitate the separation of hydrogen and tungsten-containing compounds The ratio is in the range of about 3000 to 5000 for about 10 seconds to 15 seconds. The chamber is purged with argon (or another inert gas) for 5 to 10 seconds. Repeat the cycle until the growth of the tungsten thin film reaches the specified thickness.

Some embodiments of the present invention are directed to tungsten-containing films. Such films include tungsten metal films, tungsten nitride, tungsten silicide, and tungsten silicon nitride. Tungsten-containing films can be used for many suitable purposes, including but not limited to p-metal work function layers and filling materials.

Therefore, some embodiments of the present invention are directed to fluorine-free tungsten films, which are used to fabricate metal gates in field effect transistor (FET) devices in both logic applications and memory applications. Extremely p-metal work function layer. The film grown by the process has significant benefits, including a significantly lower resistivity and higher thermal stability (which can be annealed up to 1000°C) than other films currently used as gate metals. Thermal stability is particularly important for VNAND and BWL in memory applications. One or more embodiments of the present invention are directed to tungsten thin films, which have work functions greater than about 4.6 eV or about 4.7 eV or about 4.8 eV. The work function metal can be deposited on the gate oxide of the FET. The work function metal controls the critical value of current flow. A lower threshold requires less energy to be used, so more conductive metals are better. The tungsten film deposited by a well-known process results in the film generally having a work function of about 4.45 eV.

Some embodiments of the present invention are directed to integrated circuit transistor devices that include a dielectric layer disposed on a channel. The work function metal is arranged on the dielectric layer and a filling layer consisting essentially of tungsten is deposited on the work function layer. As used in the scope of this specification and the accompanying patent application, the term "essentially composed of tungsten" used in this respect means the filling layer system More than about 95%, 98% or 99% tungsten. The work function layer of some embodiments includes one or more of Ti and TiAl. In one or more embodiments, the work function metal is substantially free of fluorine. In some embodiments, the filling layer is substantially free of fluorine. As used in the scope of this specification and the accompanying patent application, the term "substantially free of fluorine" means that there is less than about 5%, 4%, 3%, 2%, 1%, 0.5% or 0.1% in the film Fluorine atom. In some embodiments, there is no intervening layer between the work function metal and the thin film consisting essentially of tungsten.

In one or more embodiments, there is an intervening layer between the work function metal and the thin film consisting essentially of tungsten. The intervening layer may have any suitable thickness depending on the intended use of the integrated circuit transistor. In some embodiments, the intervening layer has a thickness of less than about 7Å, 6Å, 5Å, 4Å, or 3Å.

In some embodiments, the tungsten-containing film is used as a low-resistivity filling material. To achieve a completely seamless filling, periodic processing (for example, after every 10Å to 30Å film) is applied. Treatment methods include (a) alternate exposure to TiCl₄And ammonia; (b) implement TiCl₄Impregnation or (c) hydrogen direct or remote plasma exposure for 10 to 30 seconds. The treatment can be performed at the same temperature as the deposition process. The described process will deposit about 0.7Å TiN (less than 1Å TiN) to regenerate the surface and remove additional chlorides during deposition. The amount of TiN deposited in these embodiments is less than about ½ of the TiN monolayer or in the range of about 1/3 to about 1/5 of the TiN monolayer.

It has been found that the various tungsten films described can be used for: for example, (1) nucleation and film growth repeatability using silane immersion; (2) adhesion to oxide by growing one or two initial layers of tungsten silicide ; (3) Reduce roughness by impregnating with ammonia followed by impregnation with silane (to increase nucleation density); (4) By TiCl₄/NH₃Cyclic (on an oxide or oxidized surface) deposits less than about 1 Å at the interface TiN; and (5) Integrate thin TiN to provide good nucleation, adhesion and shape retention (by any suitable method and reagent deposition).

Figure 2 illustrates a schematic cross-sectional view of an embodiment of a device that can be used to perform the time domain ALD embodiment of the present invention. The equipment can be any suitable equipment for processing substrates, for example, a GEMINI ALD chamber or a Centura ALD chamber, both of which can be purchased from Applied Materials of Santa Clara, California.

The apparatus in FIG. 2 is generally a process chamber 200 having a chamber body 206 defining an internal volume 234 and a chamber cover 270 disposed on the upper surface 210 of the chamber body 206. The substrate support 212 disposed in the internal volume 234 supports the substrate 220 on the substrate receiving surface 214. The substrate support 212 (or base) is installed to the lifting motor 228 to raise or lower the substrate support 212 and the substrate 220 placed on the substrate support 212. The lifting plate 216 coupled to the lifting motor 218 is installed in the process chamber 200 and is raised or lowered through the movably arranged pin 222 of the substrate support 212. The pins 222 raise or lower the substrate 220 on the surface of the substrate support 212. In some embodiments, the substrate support 212 includes a vacuum chuck, an electrostatic chuck, or a clamping ring for fixing the substrate 220 to the substrate support 212. The opening 208 formed in the wall 204 of the chamber body 206 facilitates the passage of substrates into and out of the process chamber 200.

The substrate support 212 is heated to increase the temperature of the substrate 220 placed on the substrate support 212. For example, the substrate support 212 may be heated using an embedded heating element such as a resistance heater, or may be heated using radiant heat such as a heating lamp placed above the substrate support 212. The purge ring 224 is disposed on the substrate support 212 to define a purge channel 226 that provides purge gas to the surrounding part of the substrate 220 to prevent Sub-deposition.

The exhaust system 231 communicates with the pump channel 232 to exhaust any improper gas from the process chamber 200. The exhaust system 231 also helps maintain the desired pressure or desired pressure range inside the process chamber 200.

The gas delivery system 250 is coupled to the chamber body 206 to provide precursor, process gas, carrier gas, and/or purge gas to the process chamber 200. The gas delivery system 250 may generally include a gas panel 251 having a plurality of gas sources (six in the figure) 252, 253, 255, 265, 267, 269 and a plurality of valves (two in the figure) 257, 259 The plurality of valves 257 and 259 are coupled to one or more conduits (for example, conduits 256 and 258) to control the gas flow from the gas panel 251 to the process chamber 200. In some embodiments, a plurality of gas sources 252, 253, 255, 265, 267, 269 may be configured such that each of the plurality of gas sources 252, 253, 255, 265, 267, 269 can provide Separate gas (for example, precursor, process gas, carrier gas, purge gas, etc.), such as the gas described above with respect to Figure 1.

In some embodiments, such as depicted in Figure 2, the gas panel 251 may be arranged to combine the gas provided by the plurality of gas sources 252, 253, 255, 265, 267, 269 before reaching the process chamber 200. Wait for some gas in the gas. In some embodiments, one or more valves 257, 259 may be placed along the conduits 256, 261 to control the flow of gas provided by a plurality of gas sources 252, 253, 255, 265, 267, and 269. The valves 257 and 259 can be any type of valves, for example, on-off valves, high-speed valves, shut-off valves, etc., to facilitate pulse delivery of the gas provided by the gas panel 251. In some embodiments, for example, as depicted in Figure 2, the valves 257, 259 may be two-way valves, such as The diverter valve of the process chamber 200 is used to transfer the gas flow through the ducts 261, 273 coupled to the exhaust systems 230, 271. Each of the exhaust systems 230, 231, and 271 may be the same exhaust system or may be a partially or completely different system to prevent the reaction and/or deposition of materials in the exhaust system, and the reaction and/or deposition may be shortened The life of the exhaust system may require maintenance and/or cleaning of the components of the exhaust system (for example, pumps, ducts, valves, etc.). In such embodiments, the valves 257, 259 may be located at any position along the respective conduits 256, 258 that is suitable for selectively controlling one or more gases at the same time. For example, the valve 257 (the first valve) can be arranged downstream of the junction 263 coupling the first gas source 252 and the second gas source 255 to selectively supply gas to the process chamber 200 via the conduit 256 or via the conduit 261 transfers the gas to the exhaust system 230, as depicted in Figure 2. In addition, in some embodiments, the valve 259 (the second valve) may be arranged downstream of the fifth gas source 253 to selectively provide gas to the process chamber 200 via the conduit 258 or transfer the gas to the exhaust system via the conduit 273 271. In some embodiments, the sixth gas source 269 may be coupled to the fifth gas source 253 upstream of the valve 259 (as shown) or downstream of the valve 259 to allow the gas provided by the sixth gas source 269 to be provided together. With gas from the fifth gas source 253.

In some embodiments, one or more flow restrictors (not shown) may be positioned along the conduit 256 before the valves 257, 259 and/or after the valves 257, 259. Including one or more flow restrictors can reduce the pressure change in the conduit 256 when the gas flow is transferred to the process chamber or the transfer of the self-made process chamber, so as to deliver the uniformity provided by the gas source 252, 253, 255 Amount of gas.

In some embodiments, for example, where solid or liquid precursors are utilized, the gas delivery system 250 may also include one or more ampoules. In this case In an embodiment, one or more ampoules may be configured to allow the solid or liquid precursor to be contained and to sublime the solid or liquid precursor into a gaseous form for delivery into the process chamber 200.

Returning to FIG. 2, at least a part of the bottom surface 272 of the chamber cover 270 can be wedge-shaped from the expansion channel 274 to the surrounding part of the chamber cover 270. The expansion channel 274 improves the velocity profile of the gas flow from the expansion channel 274 across the surface of the substrate 220 (ie, from the center of the substrate to the edge of the substrate). In some embodiments, the bottom surface 272 includes one or more wedge-shaped surfaces, such as straight, concave, convex, or a combination of the foregoing. In some embodiments, the bottom surface 272 is a wedge in the shape of a funnel. The expansion channel 274 is an exemplary embodiment of a gas inlet, which is used to transport the sublimation precursor and carrier gas from the conduit 256 to the substrate 220. Other gas inlets are possible, such as funnels, non-wedge-shaped channels, nozzles, shower heads, etc.

A controller 240 such as a programmed personal computer, a workstation computer, etc. is coupled to the process chamber 200. The controller 240 illustratively includes a central processing unit (CPU) 242, a supporting circuit system 244, and a memory 246 containing associated control software 248. The controller 240 controls the operating conditions of the process performed in the process chamber, such as the ALD process described above with respect to FIG. 1. For example, the controller 240 may be configured to control the flow of various precursor gases and purge gases from the gas delivery system 250 to the process chamber 200 during different stages of the deposition cycle.

Figure 3 is a schematic cross-sectional view of a space atomic layer deposition system 300 or reactor according to one or more embodiments of the present invention. The system 300 includes a load lock chamber 301 and a processing chamber 302. The processing chamber 302 is generally dense Encapsulation, the sealable enclosure is operated under vacuum or at least low pressure. The processing chamber 302 is isolated from the load lock chamber 301 by an isolation valve 303. The isolation valve 303 seals the load lock chamber 301 and the processing chamber 302 in the closed position and allows the substrate 360 to be transferred from the load lock chamber 301 to the processing chamber 302 via the valve, and vice versa in the open position.

The system 300 includes a gas distribution assembly 310 capable of distributing one or more gases on the entire substrate 360. The gas distribution component 310 can be any suitable distribution plate well known to those skilled in the art, and the specific gas distribution component described will not be considered as limiting the scope of the present invention. The output surface of the gas distribution component 310 faces the first surface 361 of the substrate 360.

The gas distribution assembly 310 includes a plurality of gas ports and a plurality of vacuum ports, the plurality of gas ports are arranged to transmit one or more gas flows to the substrate 360, and the plurality of vacuum ports are arranged in each gas port Intermittently and arranged to transport the gas stream out of the processing chamber 302. In the detailed embodiment of FIG. 3, the gas distribution component 310 includes a first precursor injector 320, a second precursor injector 330 and a purge gas injector 340.

The injectors 320, 330, and 340 can be controlled by a system computer (not shown) such as a host computer or by a chamber-specific controller such as a programmable logic controller. The precursor injector 320 is configured to inject a continuous (or pulsed) flow of the reaction precursor of Compound A into the processing chamber 302 through a plurality of gas ports 325. The precursor injector 330 is configured to inject a continuous (or pulsed) flow of the reaction precursor of Compound B into the processing chamber 302 through a plurality of gas ports 335. The purge gas injector 340 is configured to inject a continuous (or pulsed) flow of non-reactive or purge gas to the processing chamber through a plurality of gas ports 345 Room 302. The purge gas helps remove reaction materials and reaction by-products from the processing chamber 302. The purge gas is usually an inert gas, such as nitrogen, argon, and helium. The gas port 345 is arranged between the gas port 325 and the gas port 335 to separate the compound A precursor and the compound B precursor, thereby avoiding cross-contamination between the precursors. The gas ports 325, 335, 345 and the vacuum port 355 of some embodiments are long and narrow gas ports that form channels for gas directed toward (or away from) the substrate surface, so that the channels extend across a portion of the substrate.

In another aspect, a remote plasma source (not shown) may be connected to the precursor injector 320 and the precursor injector 330 before the precursor is injected into the chamber 302. The plasma of the reactive species can be generated by applying an electric field to the compound in the remote plasma source. Any power source capable of activating the desired compound can be used. For example, the following power sources can be used: these use power sources based on DC, radio frequency (RF) and microwave (MW) discharge technologies. If an RF power source is used, the RF power source can be capacitively or inductively coupled. Activation can also be produced by heat-based techniques, gas breakdown techniques, high-intensity light sources (e.g., UV energy), or exposure to X-ray sources. Exemplary remote plasma sources are available from suppliers such as MKS Instruments and Advanced Energy Industries, Inc.

The system 300 further includes a pumping system 350 connected to the processing chamber 302. The pumping system 350 is generally configured to exhaust the gas flow out of the processing chamber 302 through one or more vacuum ports 355. The terms "vacuum port" and "pump port" can be used interchangeably. A vacuum port 355 is arranged between each gas port to discharge the gas flow out of the processing chamber 302 after the gas flow reacts with the substrate surface and further limit cross-contamination between the precursors.

The system 300 includes a plurality of partitions 363, and the plurality of partitions 363 are arranged between each port in the processing chamber 302. The lower part of each partition 363 extends close to the first surface 361 of the substrate 360. For example, the distance from the first surface 361 is about 0.5 mm or more. In this way, the lower part of the partition 363 is separated from the substrate surface 361 by a distance sufficient to allow the gas flow to flow around the lower part toward the vacuum port 355 after the gas flow reacts with the substrate surface 361. Arrow 398 indicates the direction of gas flow. Because the partitions 363 operate as a physical barrier to gas flow, the partitions 363 also limit cross-contamination between precursors. The configuration shown in the figure is only illustrative and should not be considered as limiting the scope of the present invention. Those familiar with this technology will understand that the gas distribution system shown in the figure is only one possible distribution system and other types of sprinklers can be used.

In operation, the substrate 360 is transported (for example, by a robot) to the load lock chamber 301 and placed on the shuttle 365. After opening the isolation valve 303, the shuttle 365 moves along the track 370. Once the shuttle 365 enters the processing chamber 302, the isolation valve 303 is closed to seal the processing chamber 302. The shuttle 365 then moves through the processing chamber 302 for processing. In one embodiment, the shuttle 365 moves through the chamber along a linear path.

When the substrate 360 moves through the processing chamber 302, the first surface 361 of the substrate 360 is repeatedly exposed to the compound A precursor from the gas port 325 and the compound B precursor and the compound A precursor from the gas port 335 Purge gas between the precursor and compound B. The injection of the purge gas is designed to remove unreacted material from the previous precursor before exposing the substrate surface 361 to the next precursor. After each exposure to various gas streams (for example, precursors or purge gases), the gas streams are pumped by the system 350 is evacuated via vacuum port 355. Because the vacuum ports can be placed on both sides of each gas port, the gas flow is evacuated through the vacuum ports 355 on both sides. Therefore, the gas flows from each gas port vertically downward toward the first surface 361 of the substrate 360, across the substrate surface 361 and around the lower part of the partition 363, and finally upward toward the vacuum port 355. In this way, each gas can be uniformly distributed over the entire substrate surface 361. Arrow 398 indicates the direction of gas flow. The substrate 360 can also be exposed to various gas streams while rotating. The rotation of the substrate can be used to prevent the formation of stripes in the formed layer. The rotation of the substrate can be a continuous or discrete step.

Enough space is generally provided at the end of the processing chamber 302 to ensure that the final gas port in the processing chamber 302 is completely exposed. Once the substrate 360 reaches the end of the processing chamber 302 (that is, the first surface 361 has been completely exposed to each gas port in the chamber 302), the substrate 360 returns in a direction toward the load lock chamber 301. When the substrate 360 moves backward toward the load lock chamber 301, the substrate surface may be exposed to the compound A precursor, the purge gas, and the compound B precursor again in the reverse order of the first exposure.

The extent to which the substrate surface 361 is exposed to each gas can be determined by, for example, the flow rate of each gas from the gas port and the moving speed of the substrate 360. In one embodiment, the flow rate of each gas is set so as not to remove adsorbed precursors from the surface 361 of the substrate. The width between each partition, the number of gas ports disposed on the processing chamber 302, and the number of passes of the substrate back and forth can also determine the degree of exposure of the substrate surface 361 to various gases. Therefore, the quantity and quality of the deposited film can be optimized by changing the above-mentioned factors.

In another embodiment, the system 300 may include a precursor injector 320 And precursor injector 330 and no purge gas injector 340. Therefore, when the substrate 360 moves through the processing chamber 302, the substrate surface 361 will be alternately exposed to the compound A precursor and the compound B precursor, instead of being exposed to the compound A precursor and the compound B precursor. Purify the gas.

The embodiment shown in Figure 3 has a gas distribution assembly 310 above the substrate. Although the embodiments have been described and illustrated with respect to this vertical direction, it will be understood that the opposite direction is also possible. In that case, the first surface 361 of the substrate 360 will face downward, and the flow of gas towards the substrate will be directed upward.

In yet another embodiment, the system 300 may be configured to process a plurality of substrates. In this embodiment, the system 300 may include a second load lock chamber (located at the opposite end of the load lock chamber 301) and a plurality of substrates 360 or a rotating rack processing chamber with one or more gas distribution components . The substrate 360 can be transported to the load lock chamber 301 and retrieved from the second load lock chamber. In one or more embodiments, at least one radiant heat lamp 390 is positioned to heat the second side of the substrate 360.

In some embodiments, the shuttle 365 is a base 366 for carrying the substrate 360. In general, the susceptor 366 is a carrier that helps to create a uniform temperature across the substrate. The base 366 can move bidirectionally between the load lock chamber 301 and the processing chamber 302 (from left to right and right to left with respect to the configuration in Figure 3). The base 366 has a top surface 367 for carrying the substrate 360. The susceptor 366 can be a heated susceptor so that the substrate 360 can be heated for processing. As an example, the base 366 may be heated by a radiant heat lamp 390, a heating plate, a resistive coil, or other heating device disposed under the base 366.

In another embodiment, the top surface 367 of the base 366 includes a concave A groove 368, which is configured to receive the substrate 360, as shown in FIG. 4. The base 366 is substantially thicker than the thickness of the substrate so that the base material is located under the substrate. In a detailed embodiment, the groove 368 is arranged such that when the substrate 360 is placed inside the groove 368, the first surface 361 of the substrate 360 and the top surface 367 of the base 366 are at the same level. In other words, the groove 368 of some embodiments is configured such that when the substrate 360 is placed in the groove 368, the first surface 361 of the substrate 360 does not protrude above the top surface 367 of the base 366.

Figures 5-14 illustrate a gas distribution assembly 310 according to various embodiments of the present invention. The gas distribution component 310 includes an input surface 301 and an output surface 303. The input surface 301 (shown in Figure 5) has a first reaction gas input 305 for receiving the flow of the first reaction gas A and a second reaction gas input 307 for receiving the flow of the second reaction gas B. The input surface 301 also has an input 309 for one or more purification gases and a port 311 for connecting to one or more vacuum ports.

The output surface 303 of various embodiments has a plurality of long and narrow gas ports 313. The gas ports 313 are configured to direct gas flow to the substrate, and the gas ports 313 can be positioned adjacent to the output surface 303. The elongated gas port 313 includes at least one first reactive gas port and at least one second reactive gas port. Each first reaction gas port is in flow communication with the first reaction gas input 305 to allow the first precursor to flow through the gas distribution assembly 310. Each second reaction gas port is in flow communication with the second reaction gas input 307 to allow the second precursor to flow through the gas distribution assembly 310.

As shown in Figure 6, the gas port may include a plurality of gas ports in the channel 317 Opening 315. The channel 317 is a recessed slot in the output surface of the gas distribution component. The gas flows out of the opening 315 and is directed to the surface of the substrate by the channel 317 wall. The opening 315 is illustrated as being circular, but it should be understood that the opening 315 can be any suitable shape, including but not limited to square, rectangular, and triangular. The number and size of the openings 315 can also be changed to fit more or fewer openings in each channel 317. In the detailed embodiment illustrated in Fig. 6, the purge gas (P), the first reaction gas port (A), and the second reaction gas port (B) include a plurality of openings positioned in the channel. The opening 318 associated with the vacuum port is located on the output surface 303 of the gas distribution assembly 310, not in the channel 317, but can also be located in the channel.

The specific embodiment illustrated in FIG. 6 has a combination of long and narrow gas ports, which will provide a specific sequence of gas flow to the surface of the substrate when the substrate is moved vertically along the arrow 350 to the long and narrow gas ports. Although the substrate is described as being moving, those skilled in the art will understand that the substrate can remain stationary and the gas distribution assembly 310 can move. The relative movement between the substrate and the gas distribution assembly 310 is called substrate movement. The substrate moving vertically to the long and narrow gas port will undergo the sequence of purge gas flow, first reactive gas A flow, purge gas flow, second reactive gas B flow, purge gas flow, first reactive gas A'flow, and purge gas flow. The flow of gas. The vacuum ports are between each gas flow, and the vacuum ports guide the gas flow out of the processing chamber. This produces a flow pattern according to the arrow 398 illustrated in FIG. 3.

In a specific embodiment, the gas distribution component basically consists of a leading first reactive gas port A, a second reactive gas port B, and a finishing first reactive gas port Ain sequence. As used in this context and the scope of the accompanying patent application As used, the term "consisting essentially of" means that the gas distribution assembly does not include any additional gas ports for the reaction gas. Ports for non-reactive gas (e.g., purge gas) and vacuum can be interspersed everywhere while still being within a range essentially composed of terms. For example, the gas distribution component 310 may have eight vacuum ports V and four purification ports P, but still basically consists of a leading first reactive gas port A, a second reactive gas port B, and a finishing reactive gas port A. This diverse embodiment can be referred to as an ABA setting.

Using the ABA setting ensures that the substrate moving from either direction will encounter the first reactive gas A port before encountering the second reactive gas B port. Each pass across the gas distribution assembly 310 will produce a single film of composition B. Here, the two first reactive gas A ports surround the second reactive gas B port so that the substrate moving from the top to the bottom of the diagram (relative to the gas distribution component) will meet the leading first reactive gas A and the second reaction in sequence The gas B and the finishing first reaction gas A'result in the formation of a complete layer on the substrate. The substrate returning along the same path will encounter the reaction gases in the reverse order, resulting in two layers per full cycle. The substrate moving back and forth across this gas distribution element will be exposed to the pulse sequence of AB AAB AAB(AAB)n...AABA to form a uniform thin film composition B. Exposure to the first reaction gas A at the end of the sequence is not important because there is no subsequent second reaction gas B. Those familiar with the art will understand that although the film composition is called B, B is indeed one of the surface reaction products of the reactive gas A and the reactive gas B, and only B is used for the convenience of describing the film.

As shown in Figure 7, the gas distribution assembly 310 includes a heating element 501 to excite gas species. The heating element 501 may also be referred to as a "wire" or a "hot wire". The heating element 501 is positioned between the first reactive gas port and the second reactive gas port Either or both. The heating element 501 is connected to a power cord 323 (shown in FIG. 5), and the power cord 323 is arranged so that current flows through the heating element 501 to heat the heating element 501. The heating element 501 is heated to a high temperature to excite the species in the gas passing by the adjacent heating element 501. The purpose of the wire is to generate free radical species in the gas, not to cause the temperature in the substrate to rise. The heating element 501 can be placed in a position where it is not directly exposed to the surface of the substrate, while still being able to cause the formation of free radical species in the gas. For example, if the heating element 501 is placed in the second reaction gas port, the element will cause a part of the molecules in the second reaction gas to become excited. In the excited state, the molecules have higher energy and are more likely to react with the substrate surface at a given processing temperature.

The placement of the heating element can have an effect on the amount of free radical species that contact the substrate. Placing the heating element too far from the substrate may allow a greater number of free radical species to become deactivated before contacting the surface of the substrate relative to placing it closer. Free radical species can become deactivated by contact with other free radicals, molecules in the gas stream, and gas distribution components. However, placing the heating element away from the substrate can help prevent the heating element from heating the substrate surface while still generating free radical species in the gas. The heating element 501 can be placed close enough to the surface of the substrate to ensure that the excited species exist long enough to contact the surface without causing a significant change in the local temperature of the substrate. As used in the scope of this specification and the accompanying patent application, the term "significant change in local temperature" means that the portion of the substrate adjacent to the line does not have a temperature increase greater than about 10°C. The heating element 501 can be positioned in the open channel 317 or behind the gas diffusion member as shown in FIG. 7. The embodiment of the gas diffusion component is also shown in Figure 7. The gas diffusion component has a plurality of A small spacing aperture, the small spacing aperture is placed in the outlet area of the gas port. The heating element 501 can be positioned behind the gas diffusion component, which can excite gas species without significantly changing the local temperature of the substrate. In a detailed embodiment, the wire is heated to excite the gaseous species while producing a surface temperature change of less than about 10°C. In various embodiments, the local change in the temperature of the substrate surface is less than about 7°C, 5°C, or 3°C. In certain embodiments, the local temperature change is less than about 2°C, 1°C, or 0.5°C.

The heating element can be made of any suitable material that can be raised to a high temperature in a relatively short period of time. A suitable material is a material compatible with the reaction gas. As used in the scope of this specification and the accompanying patent application, the term "compatible" used in this respect means that the heating element does not spontaneously react with the reaction gas at standard temperature and pressure. The temperature of the heating element can have an effect on the degree of radicalization of the gas species. For example, oxygen may require a temperature up to about 2000°C, while the polymer species may only require a temperature in the range of about 300°C to about 500°C. In some embodiments, the heating element can be heated to at least the following temperature: about 1000°C, 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, 1600°C, 1700°C, 1800°C, 1900°C or 2000°C . In various embodiments, the heating element can be heated to the following temperature: in the range of about 300°C to about 2000°C, or in the range of about 700°C and about 1400°C, or in the range of about 800°C to about 1300°C Within the range. The power supplied to the heating element can be adjusted or turned on and off at any point throughout the process. This allows heating of the heating element to generate excitation gas species for only part of the process.

The thickness and length of the heating element can also vary depending on the material used. Examples of suitable materials for heating elements include, but are not limited to, tungsten, tantalum, Alloys of iridium, ruthenium, nickel, chromium, graphite and the foregoing. For example, in the case where oxygen is a positively radicalized species, the use of tantalum or tungsten may be improper because these materials are sensitive to oxygen and can cause damage to the wire. In a detailed embodiment, the heating element contains tungsten.

Referring back to Figure 5, the power source can be any suitable power source capable of controlling the flow of current through the heating element. The power feedthrough 321 shown in FIG. 5 has a power cord 323 and provides both mechanical support and electrical support for the heating element and allows the heating element to be placed in the path of gas flow. The power feedthrough 321 is connected to the gas distribution assembly 310 via a mounting block 327, which may include an insulator to electrically isolate the power line 323 and the heating element from the gas distribution assembly. The heating element in the embodiment of FIG. 5 extends through the first reaction gas channel and can be an individual heating element or a single heating element surrounding the second reaction gas channel.

The heating element 501 shown in FIG. 7 extends through the channel 317 and the ends of the heating element 501 are in contact with the power lines 323 and 324. However, in one or more embodiments of the present invention, the heating element is part of a separate component that can be inserted into the channel 317 or attached to the output surface 303 of the gas distribution component 310. Therefore, referring to FIG. 8, one or more embodiments of the present invention are directed to this assembly 600. The illustrated assembly 600 includes an elongated housing 605 extending along a longitudinal axis 630. The elongated housing has an open internal area 606 that can allow gas to flow through the housing 605. The gas flow as illustrated by arrow 630 can pass through the housing in a direction substantially perpendicular to the longitudinal axis. As used in this specification and the scope of the accompanying patent application, the term "substantially vertical" means that the gas flows through the housing and around the heating element 601 at an obtuse angle. Those who are familiar with this technology will understand, The gas flow can be at an angle other than 90° to the housing and still falls within the meaning of "substantially perpendicular". In some embodiments, the gas flow is substantially perpendicular to the housing, forming the following angles: greater than about 25°, 30°, 35°, 40°, 45°, 50°, 55°, 60°, 65°, 70°, 75°, 80° or 85°. In some embodiments, the gas flow forms the following angle with respect to the housing: in the range of about 25° to about 90°, or in the range of about 45° to about 90°, or in the range of about 60° to about 90° In the range, or in the range of about 75° to about 90°, or in the range of about 80° to about 90°.

The illustrated housing 605 has flat surfaces 611 on both sides, and the side 613 has a substantially uniform thickness from one end of the housing 605 to the other end. However, those familiar with the art will understand that the shapes and approximate dimensions shown in the drawings are only exemplary and will not be regarded as limiting the scope of the present invention.

The housing 605 is made of a material that is substantially heat-resistant and expands at the temperature experienced in the processing chamber. As used in this specification and the scope of the accompanying patent application, the term "substantially heat-resistant expansion" means that the total length of the housing 605 does not change more than about 5% at the temperature required to radicalize the desired gas species. In various embodiments, the total length of the housing does not change more than about 4%, 3%, 2%, 1%, or 0.5% relative to the length of the housing 605 at room temperature. In a detailed embodiment, the housing is made of quartz or ceramic-based materials, including quartz and ceramics. As used in this specification and the accompanying patent application, the term "ceramic" refers to inorganic non-metallic materials. Suitable examples of ceramics include, but are not limited to, aluminum oxide, beryllium oxide, ceria, zirconium oxide, carbides, borides, nitrides, silicides, composite materials, oxides and non-oxides of these materials. The thickness of the heating element can be uniform or varying thickness. In some embodiments, the heating element has a cross-sectional diameter in the range of about 0.01 mm to about 5 mm. Wire. The heating elements of some embodiments have varying densities per unit length.

The heating element 601 extends from the first end 620 to the second end 622 of the elongated housing 605. As already described, the heating element 601 contains a material suitable for heating by electric current. The embodiment illustrated in FIG. 8 includes at least one electrical wire 610, shown as two wires, which are in electrical communication or electrical contact with the heating element 601 to allow current to flow through the heating element 601. The electrical lead 610 can interact with electrical contacts positioned on the gas distribution assembly. For example, the passage of the gas distribution component or the surface of the gas distribution component may include electrical contact pairs (positive and negative contacts). Each of these electrical contact pairs can be powered individually or as one or more units. In a detailed embodiment, the at least one electrical wire 610 does not substantially increase the temperature when applying current to the heating element. In certain embodiments, the at least one electrical wire 610 does not substantially cause expansion of the housing 605.

Although Figure 8 illustrates two separate electrical leads 610, it will be understood that only one electrical lead 610 can be located on either end of the housing. In this type of embodiment, the heating element 601 can extend through the housing 605 and there is a portion extending beyond the end of the housing. For example, FIG. 9 illustrates an embodiment of the assembly 700 in which the heating element 701 includes a portion 730 extending beyond the first end 720 and the second end 722 of the elongated housing 705. The extended portion 730 may serve as an electrical wire.

When heated, the heating element can expand, causing the heating element to sag. This reduces the efficiency of radicalization and allows the heating element to become closer to the substrate, which in turn heats the substrate. This sagging may be inappropriate. To minimize sagging of the heating element, one or more ends of the heating element may be held in a tensioner (not shown). The tensioner pulls up the end of the heating element to minimize sagging. The amount of tension applied to the heating element can be constant or dynamic. In a dynamic tension environment, When the heating element gets hot and becomes longer, increase the amount of tension on the heating element to prevent sagging.

The heating element can have any suitable shape and is not limited to the shape specified in the drawings. Suitable shapes include, but are not limited to, linear, sinusoidal, spiral, curved, accordion, and square waveforms. In a detailed embodiment, as shown in FIG. 9, the heating element 701 extends from the first end 720 to the second end 722 of the housing 705 in a substantially straight path. Figure 10 illustrates another embodiment of the assembly 800, in which the heating element 801 extends in a spiral path. The number and tightness of the spiral can vary and should not be regarded as limited to the shape shown in the diagram. FIG. 11 shows another assembly 900 in which two heating elements 901 extend between the first end 920 and the second end 922 of the housing 905. Figure 11 illustrates a single extension 930 for each end of the heating element 901 that is electrically connected to the heating element, but it will be understood that there may be an extension for each heating element 901. In addition, there may be any number of individual heating elements and it will be understood that the shape of each element may be different and a mixture of shapes is possible.

FIG. 12 shows another embodiment of the assembly 1000, in which the heating element 1001 is sealed in the outer cover 1002. After the current is applied, the heating element 1001 increases the temperature and heats the outer cover 1002. The outer cover 1002 is exposed to the gas flowing through the inner region 1006 of the outer cover. Embodiments of this category may have specific uses, where the heating element 1001 is incompatible with the gas flowing through the inner region 1006. In a detailed embodiment, the outer cover 1002 is a material that can be heated by the heating element 1001 without being deformed. In a particular embodiment, the outer cover 1002 contains quartz.

The components of various embodiments can be sized to fit in the channels of the gas distribution component so that the heating element can be easily added to the self-gas distribution component Or removed from the gas distribution assembly. FIG. 13 illustrates an embodiment in which the elongated housing 1105 is sized to fit in the gas port of the gas distribution assembly 310. As shown in FIG. Incorporating the heating element 501 into the housing 1105 allows the heating element 501 to be easily removed from the processing chamber for replacement or cleaning. Although the illustrated embodiment has an open channel 317, it will be understood that there may be a diffuser between the heating element and the substrate.

Referring to the bottom part of FIG. 13, another embodiment is shown in which the elongated housing 1155 is configured to be attached to the front surface 303 of the gas distribution assembly 310. The housing 1155 can be positioned such that the gas from the gas port passes through the open internal area 1156 of the housing 1155 and the components do not substantially interfere with the flow of gas from the adjacent gas port. The housing 1155 is powered by the connections 1123, 1124, as described above.

The heating element shown in Figure 14 is shown as a linear component. However, the shape of the component can be changed depending on the intended use. Figure 14 illustrates another embodiment of the present invention, in which an assembly 1200 covers two channels 317 with a single heating element 1201. The assembly 1200 includes an elongated housing 1205 having two open inner regions 1206 that are positioned on the channel 317. The heating element 1201 is connected to power lines 1223 and 1224. The heating element 1201 of this embodiment can be turned through the housing 1205 in the insulating portion 1208 where the heating element 1201 is not exposed to the flow of gas. In some embodiments, the heating element 1201 is exposed throughout the path. In other words, the open inner area can match the shape of the housing to the portion of the heating element 1201 that is not positioned in front of the gas port.

In the embodiment category illustrated in Figure 14, the power lines 1223, 1224 have opposite polarities to allow current to flow. Therefore, one power cord will be positive and the other One power line will be negative. This setting can be relatively easy to set up, and a single power source is connected to both power lines 1223 and 1224. A single power source (not shown) may include a mechanism to control the current flowing through the wire, such as a potentiometer.

Some embodiments of the gas distribution assembly include a plurality of elongated gas ports consisting essentially of: at least two repeating units of alternating first reactive gas A port and second reactive gas B port in sequence, followed by finishing The first reaction gas A'port. In other words, the combination of the first reactive gas A port and the second reactive gas B port (the combination may be referred to as the AB unit) and the finishing first reactive gas A'port are repeated at least twice. Those familiar with the art will understand that there may be purification, vacuum, and multiple openings in the gas distribution assembly.

In some embodiments, one or more layers may be formed during a plasma enhanced atomic layer deposition (PEALD) process. In some processes, plasma is used to provide enough energy to promote the species to enter the surface reaction to become a good and possible excited state. The introduction of plasma into the process can be continuous or pulsed. In some embodiments, sequential pulses of precursor (or reactive gas) and plasma are used to treat the layer. In some embodiments, the reagent can be ionized locally (ie, within the treatment zone) or remotely (ie, outside the treatment zone). In some embodiments, remote ionization may occur upstream of the deposition chamber so that ions or other high-energy or luminescent species do not directly contact the deposited film. In some PEALD processes, plasma is generated from outside the processing chamber, such as by a remote plasma generator system. Plasma can be produced by any suitable plasma production process or technique known to those skilled in the art. For example, plasma can be generated by one or more of a microwave (MW) frequency generator or a radio frequency (RF) generator. The frequency of the plasma can be adjusted depending on the specific reactive species being used. Suitable frequencies include but not Limited to 2MHz, 13.56MHz, 40MHz, 60MHz and 100MHz. Although plasma can be used during the deposition process disclosed herein, it should be noted that plasma may not be required. In fact, other embodiments relate to the deposition process under extremely mild conditions without plasma.

The tungsten nucleation layer described above has shown its specific utility when integrated with the traditional bulk filling technology to form a characteristic structure with excellent film properties. The integration scheme may include an ALD process or a pulsed CVD process to deposit the nucleation layer, and the entire layer may be deposited by a CVD process or a PVD process. The integrated processing system that can execute this integrated solution includes Endura^TMProcessing system, Endura SL^TMProcessing system, Centura^TMProcessing system and Producer^TMTreatment systems, each of which can be purchased from Applied Materials, Inc., Santa Clara, California. Any of these systems can be configured to include at least one ALD or pulsed CVD chamber for depositing the nucleation layer and at least one CVD chamber or PVD chamber for bulk filling.

Figure 15A is a schematic top view of an exemplary multi-chamber processing system 1500. A similar multi-chamber processing system is disclosed in commonly assigned US Patent No. 5,186,718, which is incorporated herein by reference. The system 1500 generally includes load lock chambers 1502, 1504, which are used to transfer substrates into and out of the system 1500. Generally, because the system 1500 is under vacuum, the load lock chambers 1502, 1504 can "pump down" the substrate introduced into the system 1500. The first robot 1510 can transfer substrates between the load lock chambers 1502, 1504 and a first set of one or more substrate processing chambers 1512, 1514, 1516, 1518 (four are shown). Each processing chamber 1512, 1514, 1516, 1518 can be equipped to perform a certain number of Various substrate processing operations, such as cyclic layer deposition, CVD, PVD, etching, pre-cleaning, degassing, orientation, and other substrate manufacturing processes. The first robot 1510 also transfers the substrate to/from the one or more transfer chambers 1522, 1524.

The transfer chamber 1522, 1524 is used to maintain ultra-high vacuum conditions while allowing the substrate to be transferred in the system 1500. The second robot 1530 can transfer substrates between the transfer chamber 1522, 1524 and a second set of one or more processing chambers 1532, 1534, 1536, 1538. Similar to the processing chambers 1512, 1514, 1516, 1518, the processing chambers 1532, 1534, 1536, 1538 can be equipped to perform various substrate processing operations, such as cyclic deposition, CVD, PVD, etching, pre-cleaning, degassing, and orientation . If any of the substrate processing chambers 1512, 1514, 1516, 1518, 1532, 1534, 1536, 1538 is unnecessary for the specific process to be performed by the system 1500, it can be removed from the system 1500.

In one configuration, each processing chamber 1532 and 1538 can be a cyclic deposition chamber adapted to deposit the nucleation layer; each processing chamber 1534 and 1536 can be a cyclic deposition chamber, chemical gas adapted to form an integral layer A phase deposition chamber or a physical vapor deposition chamber; each processing chamber 1512 and 1514 can be a physical vapor deposition chamber, a chemical vapor deposition chamber or a cyclic deposition chamber adapted to deposit dielectric layers; and each A processing chamber 1516 and 1518 may be an etching chamber equipped to etch apertures or openings of interconnect features. This specific configuration of the system 1500 is provided to illustrate the present invention and should not be used to limit the scope of the present invention.

Another integrated system may include nucleation deposition in a single chamber and bulk filling deposition. Can be used to set up in the cyclic deposition mode as well as the conventional The CVD mode operates in both chambers. An example of this chamber is described in commonly assigned U.S. Patent Application No. 10/016,300 filed on December 12, 2001, which is incorporated herein by reference.

In another integration scheme, one or more cyclic deposition nucleation chambers are integrated on the first processing system, while one or more monolithic layer deposition chambers are integrated on the second processing system. In this setup, the substrate is processed for the first time in the first system where the nucleation layer is deposited on the substrate. After that, the substrate is moved to the second processing system where the bulk deposition occurs.

Figure 15B is a schematic top view of an exemplary multi-chamber processing system 1550. The system 1550 generally includes a load lock chamber 1552, 1554 for transferring substrates into the system 1550 and transferring substrates from the system 1550. Generally, because the system 1550 is under vacuum, the load lock chamber 1552, 1554 can "pump down" the substrate introduced into the system 1550. The robot 1560 can transfer substrates between the load lock chamber 1552, 1554 and the substrate processing chambers 1562, 1564, 1566, 1568, 1570, and 1572. Each processing chamber 1562, 1564, 1566, 1568, 1570, and 1572 can be equipped to perform a certain number of substrate processing operations, such as cyclic layer deposition, CVD, PVD, etching, pre-cleaning, degassing, heating, orientation, and others Substrate manufacturing process. The robot 1560 also transfers the substrate to/from the transfer chamber 1556. Any of the substrate processing chambers 1562, 1564, 1566, 1568, 1570, and 1572 can be removed from the system 1550 if it is unnecessary for the specific process to be performed by the system 1550.

In one configuration, each processing chamber 1564 and 1570 can be a cyclic deposition chamber adapted to deposit the nucleation layer; each processing chamber 1566 and 1568 It can be a cyclic deposition chamber, a chemical vapor deposition chamber or a physical vapor deposition chamber adapted to form an integrally filled deposition layer. This specific configuration of the system 1550 is provided to illustrate the present invention and should not be used to limit the scope of the present invention.

Alternatively, a rotating rack type batch processing system with multiple stations in a single chamber can be adapted to incorporate nucleation and bulk layer deposition into a single processing system. In this processing system, a clean gas curtain such as an argon gas curtain can be established between each station to create a micro or small environment at each station. The substrates are sequentially loaded into the system and then rotated through each station and at least partially processed at each station. For example, the substrate may be exposed to a cyclic deposition nucleation step at the first station and then exposed to a localized bulk fill CVD step at each subsequent station. Alternatively, nucleation can occur at more than one station and overall filling can occur at one or more stations. Furthermore, the nucleation layer and the overall layer can be deposited in a separate rotating rack type system. In another aspect, the impregnation and nucleation steps are completed in one rotating rack, while the overall steps are performed on another rotating rack, where the two rotating racks are part of the same process system. Each plate can be temperature controlled to provide at least some process control at each station. However, the process pressure usually remains the same between stations because the stations are housed in a single chamber. Some pressure control can be used in the micro or small environment present at each station due to the inert gas curtain.

Regardless of the integration scheme, the nucleation layer is usually deposited to a thickness in the range from about 10 Å to about 200 Å, and the overall layer has the following thickness: in the range from about 100 Å to about 10000 Å, preferably from about 100 Å to about 10000 Å. Within the range of 1000Å to about 5000Å. However, the thickness of these films can vary depending on the feature size and aspect ratio of a given application. Therefore, the film is properly Adjust the size to fit the geometry of a given application. The following are some exemplary geometries and applications that can benefit from nucleation layers deposited according to the embodiments described herein. The following description is intended for illustrative purposes only and is not intended to limit the use of the present invention.

Figure 16 illustrates a cross-section of a processing chamber 1600 that includes a gas distribution assembly 1620 and a base assembly 1640, also known as a syringe or syringe assembly. The gas distribution assembly 1620 is any type of gas delivery device used in the processing chamber. The gas distribution assembly 1620 includes a front surface 1621 that faces the base assembly 1640. The front surface 1621 may have any number or types of openings to convey gas flow toward the base assembly 1640. The gas distribution assembly 1620 also includes an outer edge 1624, which is shown to be substantially circular in the embodiment.

The specific type of gas distribution element 1620 used may vary depending on the specific process being used. The embodiments of the present invention can be used with any type of processing system in which the gap between the base and the gas distribution assembly is controlled. Although various types of gas distribution components (for example, shower heads) can be used, embodiments of the present invention may be particularly useful for spatial ALD gas distribution components that have a plurality of substantially parallel gas channels. As used in this specification and the scope of the accompanying patent application, the term "substantially parallel" means that the long and narrow axes of the gas channels extend in the same general direction. There may be minor defects in the parallelism of the gas channels. The plurality of substantially parallel gas channels may include at least one first reaction gas A channel, at least one second reaction gas B channel, at least one purge gas P channel, and/or at least one vacuum V channel. Flows from one or more first reaction gas A channels, one or more The gas system of a plurality of second reaction gas B channels and one or more purge gas P channels is guided to the top surface of the wafer. Some gas flow moves horizontally across the surface of the wafer and exits the processing area via one or more purge gas P channels. The substrate moving from one end of the gas distribution component to the other end will be sequentially exposed to each process gas, thereby forming a layer on the surface of the substrate.

In some embodiments, the gas distribution assembly 1620 is a rigid fixed body composed of a single syringe unit. In one or more embodiments, the gas distribution assembly 1620 is composed of a plurality of individual sectors 1622 (see Figure 17). A gas distribution assembly with a single-piece body or a multi-sector body can be used with the various embodiments of the invention described.

The base assembly 1640 is positioned below the gas distribution assembly 1620. The base assembly 1640 includes an edge 1644, a top surface 1641, and a bottom surface 1643 to define a thickness. The top surface 1641 may include at least one groove 1642 that is sized to support the substrate for processing. The groove 1642 can be any suitable shape and size depending on the shape and size of the wafer 1660 being processed. In the embodiment shown in FIG. 16, the groove 1642 has a flat bottom to support the bottom of the wafer, but it should be understood that the bottom of the groove can vary. In some embodiments, the groove has stepped areas around the outer peripheral edge of the groove, and the stepped areas are sized to support the outer peripheral edge of the wafer. The amount of the outer peripheral edge of the wafer supported by the step can vary depending on, for example, the thickness of the wafer and the presence of features already present on the backside of the wafer.

In some embodiments, as shown in FIG. 16, the groove 1642 in the top surface 1641 of the base assembly 1640 is sized so that the wafer 1660 supported in the groove 1642 has the same top surface 1641 as the base 1640. essentially Coplanar top surface 1661. As used in this specification and the scope of the accompanying patent application, the term "substantially coplanar" means that the top surface of the wafer and the top surface of the base assembly are coplanar within ±0.2 mm. In some embodiments, the top surface is coplanar within ±0.15mm, ±0.10mm, or ±0.05mm.

The base assembly 1640 of FIG. 16 includes a pillar 1690 that can raise, lower, and rotate the base assembly 1640. The base assembly may include heaters or gas lines or electrical components in the center of the pillar 1690. The pillar 1690 may be the main means to increase or decrease the gap between the base assembly 1640 and the gas distribution assembly 1620. The base assembly 1640 may also include fine adjustment actuators 1662, which can fine-tune the base assembly 1640 to create a desired gap 1670 between the base assembly 1640 and the gas injector assembly 1620.

In some embodiments, the gap 1670 distance during processing is: in the range of about 0.1 mm to about 5.0 mm, or in the range of about 0.1 mm to about 3.0 mm, or in the range of about 0.1 mm to about 2.0 mm In the range, or in the range of about 0.2mm to about 1.8mm, or in the range of about 0.3mm to about 1.7mm, or in the range of about 0.4mm to about 1.6mm, or in the range of about 0.5mm to about 1.5 mm, or about 0.6mm to about 1.4mm, or about 0.7mm to about 1.3mm, or about 0.8mm to about 1.2mm, or about 0.9mm to Within the range of about 1.1mm, or about 1mm.

The processing chamber 1600 shown in FIGS. 16 and 17 is a rotating rack type chamber in which the base assembly 1640 can hold a plurality of wafers 1660. As shown in Figure 17, the gas distribution assembly 1620 may include a plurality of individual injections The injector unit 1622, each injector unit 1622 can deposit a thin film on the wafer when the wafer moves under the injector unit. Four generally pie-shaped syringe units 1622 are shown positioned on approximately opposite sides of the base assembly 1640 and above the base assembly 1640. The number of syringe units 1622 is shown for illustrative purposes only. It should be understood that more or fewer syringe units 1622 may be included. In some embodiments, there are a sufficient number of pie-shaped syringe units 1622 to form a shape that conforms to the shape of the base assembly 1640. In some embodiments, each of the individual pie-shaped syringe units 1622 can be independently moved, removed, and/or replaced without affecting any other syringe units 1622. For example, a section may be elevated to allow a robot to access the area between the base assembly 1640 and the gas distribution assembly 1620 to load/unload the wafer 1660.

Similarly, although not shown, the base assembly 1640 may be composed of a plurality of individual blocks or units. A plurality of units can be generally pie-shaped and can be assembled together to form a base assembly having a top surface and a bottom surface.

The size of the base assembly 1640 can vary depending on the specific processing chamber and the size of the wafer to be processed. In some embodiments, the base assembly is sized to support at least three wafers. In one or more embodiments, the base assembly is sized to support at least 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 1, 14, 15, 16 or more wafers. The wafer can be any size wafer, including but not limited to 150mm wafer, 200mm wafer, 300mm wafer and 450mm wafer. The diameter of the base assembly can also vary. In some embodiments, the base component has the following diameter: in the range of about 0.75 meters to about 2 meters, or in the range of about 1 meter to about 1.75 meters, or in the range of about 1.25 meters to about 1.25 meters. Within 1.75 meters Or about 1.5 meters.

A processing chamber with multiple gas injectors can be used to process multiple wafers at the same time so that the wafers undergo the same process flow. For example, as shown in FIG. 17, the processing chamber 1600 has four gas injector units 1622 and four wafers 1660. The drawings of the four injector units 1622 are only representative and have been selected to allow for an easier view and description of the manufacturing process. Those skilled in the art will understand that the gas distribution assembly may be a single component and may have approximately the same size and/or shape as the base assembly. At the beginning of the process, the wafer 1660 may be positioned between the injector units 1622. Rotate the base assembly 1640 1617 45° will cause each wafer 1660 between the injector units 1622 to be moved to the injector unit 1622 for thin film deposition, as illustrated by the dotted circle under the injector assembly 1622. The additional 45° rotation will move the wafer 1660 away from the injector assembly 1622. For spatial ALD injectors, the thin film is deposited on the wafer during the movement of the wafer relative to the injector assembly. In some embodiments, the base assembly 1640 rotates incrementally, which prevents the wafer 1660 from stopping under the injector unit 1622. The numbers of the wafer 1660 and the injector unit 1622 can be the same or different. In some embodiments, when there are gas distribution components, there are the same number of wafers being processed. In one or more embodiments, the number of wafers being processed is a fraction or integer multiple of the number of gas distribution components. For example, if there are four gas distribution components, there are 4x wafers being processed, where x is an integer value greater than or equal to one.

The processing chamber 1600 illustrated in Figure 17 represents only one possible configuration and should not be considered as limiting the scope of the present invention. Here, the processing chamber 1600 includes a plurality of gas distribution components 1620. In the illustrated embodiment, there are four The gas distribution assembly 1622 is evenly spaced around the processing chamber 1600. The illustrated processing chamber 1600 is octagonal, however, those skilled in the art will understand that this is a possible shape and should not be considered as limiting the scope of the present invention. The illustrated gas distribution component 1620 is trapezoidal, but those skilled in the art will understand that the gas distribution component can be a single circular part or consist of a plurality of pie-shaped sections with radial inner and/or outer peripheral edges. composition.

The embodiment illustrated in Figure 17 includes a load lock chamber 1680 or an auxiliary chamber such as a buffer station. This chamber 1680 is connected to one side of the processing chamber 1600 to allow the substrate 1660 to be loaded/unloaded from the chamber 1600, for example. The wafer robot may be positioned in the chamber 1680 to move the substrate.

The rotation of the rotating material rack (for example, the base assembly 1640) can be continuous or discontinuous. In continuous processing, the wafer is continuously rotated to expose the wafer to each injector in turn. In a discontinuous process, the wafer can be moved to the injector area and stopped, and then moved to the area between the injectors 1684 and stopped. For example, the rotating rack can be rotated so that the wafer moves from the inter-injector area across the injector (or stops adjacent to the injector) and continues to the next inter-injector area where the wafer can be paused again. The pause between injectors can provide time for additional processing steps (e.g., exposure to plasma) between the deposition of each layer.

According to one or more embodiments, the substrate is continuously under vacuum or "load lock" conditions and is not exposed to ambient air when moving from one chamber to the next. Therefore, the transfer chamber is under vacuum and is "pumped down" under vacuum pressure. The inert gas may be present in the processing chamber or the transfer chamber. In some embodiments, the inert gas system is used as the purge gas to After the silicon layer is formed on the surface of the board, some or all of the reactants are removed. According to one or more embodiments, a purge gas is injected at the outlet of the deposition chamber to prevent the reactants from moving from the deposition chamber to the transfer chamber and/or additional processing chambers. Therefore, the flow of inert gas forms a curtain at the outlet of the chamber.

The substrates can be processed in a single substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. The substrates can also be processed in a continuous manner, such as a conveyor belt system, in which multiple substrates are individually loaded into the first part of the chamber, move through the chamber, and unloaded from the second part of the chamber. The shape of the chamber and the associated conveyor belt system can form a straight path or a curved path. In addition, the processing chamber may be a rotating rack, in which a plurality of substrates move around a central axis and are exposed to processes such as deposition, etching, annealing, and cleaning along the entire path of the rotating rack.

During processing, the substrate can be heated or cooled. This heating or cooling can be achieved by any suitable means, including but not limited to changing the temperature of the substrate support and allowing the heated or cooled gas to flow to the surface of the substrate. In some embodiments, the substrate support includes a heater/cooler that can be controlled to thermally change the temperature of the substrate. In one or more embodiments, the gas (or reactive gas or inert gas) being used is heated or cooled to locally change the substrate temperature. In some embodiments, the heater/cooler is positioned in the chamber adjacent to the surface of the substrate to convectively change the temperature of the substrate.

The substrate can also be fixed or rotating during processing. The rotating substrate can be rotated continuously or in discrete steps. For example, the substrate can be rotated throughout the entire process, or the substrate can be rotated slightly between exposure to different reaction gases or purge gases. Rotate the substrate during processing (continuously or press Step ground) can help produce more uniform deposition or etching by minimizing, for example, the effects of local variability in gas flow geometry.

The first embodiment is directed to a processing method that includes sequentially exposing a substrate to a first reaction gas and a second reaction gas including a tungsten-containing compound to form a tungsten-containing film, the tungsten-containing compound including an empirical formula W_xCl_5xThe compound.

In the second embodiment, the first embodiment is modified, wherein the second reaction gas includes a hydrogen-containing compound and the tungsten-containing film is a tungsten film.

In the third embodiment, the first embodiment or the second embodiment is modified, wherein the second reaction gas includes a nitrogen-containing compound and the tungsten-containing film includes tungsten nitride.

In the fourth embodiment, any of the first to third embodiments is modified, wherein the second reaction gas includes a silicon-containing compound and the tungsten-containing film includes tungsten silicide (WSi_x)。

In the fifth embodiment, the first embodiment or the fourth embodiment is modified in which the second reaction gas further contains hydrogen.

In the sixth embodiment, any of the first to fifth embodiments is modified, wherein the second reaction gas includes a mixture of a silicon-containing compound and a nitrogen-containing compound, and the tungsten-containing film includes tungsten silicon nitride (WSi_xN_y)。

In the seventh embodiment, any of the first to sixth embodiments is modified, in which the substrate is maintained at a temperature less than about 475°C.

In the eighth embodiment, any one of the first embodiment, the second embodiment, or the seventh embodiment is modified in which the tungsten-containing thin film is basically composed of tungsten.

In the ninth embodiment, the eighth embodiment is modified in which the substrate includes a work function metal.

In the tenth embodiment, the ninth embodiment is modified in which the work function metal contains Ti.

In the eleventh embodiment, any one of the ninth embodiment or the tenth embodiment is modified, wherein the work function metal includes TiAl.

In the twelfth embodiment, any of the eighth to eleventh embodiments is modified in which there is no intervening layer between the work function metal and the thin film consisting essentially of tungsten.

In the thirteenth embodiment, any of the eighth to eleventh embodiments is modified, in which there is an intervening layer between the work function metal and the thin film consisting essentially of tungsten, and the intervening layer has less than about The thickness of 5 angstroms.

The fourteenth embodiment of the present invention is directed to a processing method including: positioning a substrate in a processing chamber; and sequentially exposing at least a portion of the substrate to a first reaction at a temperature less than or equal to about 475°C Gas and a second reaction gas to form a tungsten-containing film. The first reaction gas includes tungsten pentachloride and has an empirical formula W_xCl5_xOne or more of its compounds or tungsten hexachloride.

In the fifteenth embodiment, the fourteenth embodiment is modified, wherein the second reaction gas includes a hydrogen-containing compound and the tungsten-containing thin film is a tungsten thin film.

In the sixteenth embodiment, any one of the fourteenth embodiment or the fifteenth embodiment is modified, wherein the second reaction gas includes a nitrogen-containing compound and the tungsten-containing film includes tungsten nitride.

In the seventeenth embodiment, any one of the fourteenth embodiment to the sixteenth embodiment is modified, wherein the second reaction gas includes a silicon-containing compound and the tungsten-containing film includes tungsten silicide (WSi_x)。

In the eighteenth embodiment, the seventeenth embodiment is modified in which the second reaction gas further contains hydrogen.

In the nineteenth embodiment, any one of the fourteenth to eighteenth embodiments is modified, wherein the second reaction gas includes a mixture of a silicon-containing compound and a nitrogen-containing compound, and the tungsten-containing thin film includes tungsten silicon nitrogen Compound (WSi_xN_y)。

In the twentieth embodiment, any one of the fourteenth embodiment to the nineteenth embodiment is modified, wherein the substrate includes a metal layer before depositing the tungsten-containing thin film.

In the twenty-first embodiment, any one of the fourteenth embodiment to the twentieth embodiment is modified, wherein before depositing the tungsten-containing thin film, the substrate includes an oxide layer and the method further includes a temperature of about 5 torr to about 20 torr. The substrate is impregnated with disilane or a mixture of hydrogen and silane at a partial pressure within the range of the torr.

In the twenty-second embodiment, any one of the fourteenth embodiment to the twenty-first embodiment is modified, wherein the tungsten-containing thin film is operated at a rate in the range of about 0.2 Å/cycle and about 3 Å/cycle Grow.

The twenty-third embodiment of the present invention is directed to a kind of deposited WSi_xThin film method. The method includes: positioning a substrate in a processing chamber; and sequentially exposing at least a part of the substrate to a first reaction gas and a second reaction gas at a temperature less than or equal to about 475°C to form WSi_xA thin film, where the first reaction gas contains tungsten pentachloride and has an empirical formula W_xCl_5xThe second reaction gas contains silicon-containing gas, and the ratio of silicon-containing gas to tungsten-containing gas is in the range of about 100:2 and about 100:0.2.

In the twenty-fourth embodiment, the twenty-third embodiment is modified, wherein the silicon-containing gas includes one or more of silane and disilane, and the second reaction gas It further contains hydrogen.

In the twenty-fifth embodiment, any one of the twenty-third embodiment to the twenty-fourth embodiment is modified to further include exposing at least a part of the substrate to a hydrogen-containing gas instead of silicon-containing gas in an alternating cycle gas.

In the twenty-sixth embodiment, the twenty-fifth embodiment is modified in which the substrate is exposed to the hydrogen-containing gas before being exposed to the silicon-containing gas.

The twenty-seventh embodiment of the present invention is directed to an integrated circuit transistor device. The integrated circuit transistor device includes: a dielectric layer arranged on a channel; a work function metal arranged on the dielectric layer; and an arrangement The filling layer on the work function layer is basically composed of W.

In the twenty-eighth embodiment, the twenty-seventh embodiment is modified in which the work function layer contains Ti.

In the twenty-ninth embodiment, any one of the twenty-seventh embodiment to the twenty-eighth embodiment is modified in which the work function layer includes TiAl.

In the thirtieth embodiment, any one of the twenty-eighth embodiment or the twenty-ninth embodiment is modified, in which the work function metal is substantially free of fluorine.

In the thirty-first embodiment, any one of the twenty-seventh embodiment to the thirtieth embodiment is modified, wherein the filling layer is substantially free of fluorine.

In the thirty-second embodiment, any one of the twenty-seventh embodiment to the thirty-first embodiment is modified, wherein the filling layer consisting essentially of W is an ALD W layer.

In the thirty-third embodiment, the thirty-second embodiment is modified, in which the ALD W layer is formed by W_xCl_5xAnd the second reaction gas containing the hydrogen-containing compound is sequentially exposed and formed.

In the thirty-fourth embodiment, any one of the twenty-seventh embodiment to the thirty-third embodiment is modified in which there is no intervening layer between the work function metal and the thin film consisting essentially of tungsten.

In the thirty-fifth embodiment, any one of the twenty-seventh embodiment to the thirty-third embodiment is modified, in which there is an intervening layer between the work function metal and the thin film consisting essentially of tungsten, the intervening The layer has a thickness of less than about 5 angstroms.

In the thirty-sixth embodiment, any one of the twenty-seventh embodiment to the thirty-fifth embodiment is modified, wherein the filling layer is CVD W, and the CVD W is formed by W_xCl5_xAnd the second reaction gas containing the hydrogen-containing compound is simultaneously exposed and formed.

The thirty-seventh embodiment of the present invention is directed to a processing method that includes sequentially exposing at least a part of the substrate in the processing chamber to the empirical WCl₅Or WCl₆The first reaction gas containing tungsten compound and the second reaction gas containing hydrogen radicals form a tungsten-containing film.

In the thirty-eighth embodiment, the thirty-seventh embodiment further includes generating hydrogen radicals from hydrogen.

In the thirty-ninth embodiment, the thirty-eighth embodiment is modified, wherein generating hydrogen radicals from hydrogen includes passing hydrogen gas through a heating element having a temperature sufficient to generate hydrogen radicals.

In the fortieth embodiment, the thirty-ninth embodiment further includes heating the heating element to a temperature sufficient to generate hydrogen radicals.

In the forty-first embodiment, the fortieth embodiment is modified, wherein heating the heating element includes providing current to flow through the heating element.

In the forty-second embodiment, any of the fortieth embodiment and the forty-first embodiment further includes applying dynamic tension to the end of the heating element to prevent the heating element from being at a temperature sufficient to generate hydrogen radicals Sagging.

In the forty-third embodiment, any one of the fortieth embodiment to the forty-second embodiment is modified, in which the heating element is contained in a shell that is substantially heat-resistant and expandable.

In the forty-fourth embodiment, any one of the thirty-seventh embodiment to the forty-third embodiment is modified, wherein the first reaction gas and the second reaction gas system flow into the processing chamber at the same time.

In the forty-fifth embodiment, any one of the thirty-seventh embodiment to the forty-fourth embodiment is modified, in which the first reaction gas and the second reaction gas system pass through a gas distribution element containing adjacent long and narrow gas ports The first reaction gas and the second reaction gas system flowing into the processing chamber and passing through different long and narrow gas ports are separated by at least one of the purge gas port and the vacuum port.

In the forty-sixth embodiment, any one of the thirty-ninth embodiment to the forty-fifth embodiment is modified, wherein the heating element is positioned in the second reaction gas port.

In the forty-seventh embodiment, any one of the thirty-ninth embodiment to the forty-fifth embodiment is modified, in which the heating element is contained in a casing that is substantially heat-resistant and expandable.

In the forty-eighth embodiment, the forty-seventh embodiment is modified, in which a casing is attached to the front surface of the gas distribution component, so that the second reaction gas flowing from the second reaction gas port flows through the casing and around the heating element.

In the forty-ninth embodiment, the forty-fifth to the forty-eighth Any of the embodiments further includes moving the substrate relative to the gas distribution assembly so as to expose each part of the substrate to a gas flow, the gas flow consisting essentially of the first reaction gas and the second reaction gas in sequence.

In the fiftieth embodiment, any one of the thirty-seventh embodiment to the forty-ninth embodiment is modified, wherein the substrate is maintained at a temperature less than about 475°C.

The fifty-first embodiment is directed to a processing method. The processing method includes: positioning a substrate in a processing chamber that includes a gas distribution assembly. The gas distribution assembly includes a plurality of elongated gas ports, and the plurality of elongated gas ports includes a first The reaction gas port and the second reaction gas port, the first reaction gas port and the inclusion of empirical WCl₅Or WCl₆The first reaction gas containing the tungsten compound is in fluid communication and the second reaction gas port is in fluid communication with the second reaction gas containing hydrogen, and the gas distribution component allows both the first reaction gas and the second reaction gas to flow into the processing chamber at the same time; Passing the second reaction gas through the heating element to generate hydrogen radicals in the second reaction gas; and sequentially exposing at least a part of the substrate to the hydrogen radicals in the first reaction gas and the second reaction gas to form tungsten on the substrate film.

In the fifty-second embodiment, the fifty-first embodiment is modified, in which the heating element is contained in a substantially heat-resistant expansion housing, and the housing is attached to the front surface of the gas distribution assembly so that the second reaction gas flows through the housing.

In the fifty-third embodiment, any one of the fifty-first embodiment to the fifty-second embodiment is modified, wherein the substrate includes a metal layer before depositing the tungsten thin film.

In the fifty-fourth embodiment, the fifty-first embodiment to the fifth embodiment are modified Any of the thirteen embodiments, wherein before depositing the tungsten thin film, the substrate comprises an oxide layer and the method further comprises impregnating with disilane or a mixture of hydrogen and silane at a partial pressure in the range of about 5 torr to about 20 torr Substrate.

In the fifty-fifth embodiment, any one of the fifty-first embodiment to the fifty-fourth embodiment is modified in which the tungsten thin film is grown at a rate in the range of about 0.2 Å/cycle and about 3 Å/cycle .

In the fifty-sixth embodiment, any one of the fifty-first embodiment to the fifty-fifth embodiment is modified in which at least a part of the substrate is sequentially exposed to one of the first reaction gas and the second reaction gas Hydrogen radicals include: moving the substrate relative to the gas distribution component so as to expose each part of the substrate to a gas flow consisting essentially of a first reactive gas and hydrogen radicals in sequence.

The fifty-seventh embodiment of the present invention is directed to a processing method comprising: impregnating a substrate with silane; and sequentially exposing the substrate previously impregnated with silane to a first reaction gas and a second reaction gas to form a tungsten film , The first reaction gas includes a tungsten-containing compound and hydrogen, and the tungsten-containing compound includes an empirical formula W_xCl_5xFor the compound, the second reaction gas contains a reducing agent.

In the fifty-eighth embodiment, the fifty-seventh embodiment is modified in which the second reaction gas contains a hydrogen-containing compound.

In the fifty-ninth embodiment, any one of the fifty-seventh embodiment to the fifty-eighth embodiment is modified, wherein the substrate is maintained at a temperature greater than about 350°C.

In the sixtieth embodiment, any one of the fifty-seventh embodiment to the fifty-ninth embodiment is modified, wherein when the tungsten thin film has a thickness of about 70Å, the tungsten thin film has a grain size greater than about 60Å .

In the sixty-first embodiment, any one of the fifty-seventh embodiment to the sixtieth embodiment is modified, wherein when the tungsten film has a thickness of about 200Å, the tungsten film has a resistance of less than about 30μΩcm Rate.

In the sixty-second embodiment, any one of the fifty-seventh embodiment to the sixty-first embodiment is modified, wherein the first reaction gas contains more hydrogen atoms than tungsten atoms.

In the sixty-third embodiment, any one of the fifty-seventh embodiment to the sixty-second embodiment is modified, wherein the first reaction gas is contained in a ratio in the range of about 1:2 to 1:20 The presence of tungsten compounds and hydrogen.

The sixty-fourth embodiment of the present invention is directed to a method of forming a conformal tungsten thin film, which includes: exposing the surface to a first reaction gas containing a tungsten compound for a first time and a second reaction gas containing hydrogen for a period of time. The second time is to deposit the tungsten film, and the first time and the second time are both less than about 2 seconds.

In the sixty-fifth embodiment, the sixty-fourth embodiment is modified, in which the tungsten thin film is grown at a rate of less than about 1 Å/cycle.

In the sixty-sixth embodiment, any one of the sixty-fourth embodiment to the sixty-fifth embodiment is modified, wherein the tungsten thin film is grown at a rate of less than about 0.8 Å/cycle.

The sixty-eighth embodiment is directed to an integrated circuit transistor device. The integrated circuit transistor device includes: a dielectric layer disposed on a channel; and a work function layer consisting of tungsten on the dielectric layer.

The sixty-ninth embodiment of the present invention is directed to a processing method that includes: (a) depositing the thickness of tungsten as a filling material on the work function material in the transistor; (b) processing the deposited tungsten thin film; and (c) Repeat (a) and (b) to form Filling with a desired thickness of tungsten, wherein the treatment of the tungsten thin film includes one or more of the following: (1) sequentially exposing the filling material to titanium tetrachloride and ammonia; (2) immersing the filling material in titanium tetrachloride And (3) exposing the filling material to the hydrogen plasma for a time in the range of about 10 seconds to about 30 seconds.

In the sixty-ninth embodiment, the sixty-eighth embodiment is modified, wherein the thickness of the tungsten deposited as the filling material in (a) is in the range of about 10Å to about 30Å.

In the seventieth embodiment, any one of the sixty-eighth embodiment to the sixty-ninth embodiment is modified, wherein the amount of TiN is less than about ½ the thickness of the single layer.

Although the present invention has been described herein with reference to specific embodiments, it should be understood that these embodiments only illustrate the principles and applications of the present invention. It will be obvious to those familiar with the art that various modifications and changes can be made to the method and equipment of the present invention without departing from the spirit and scope of the present invention. Therefore, the present invention intends to include modifications and changes within the scope of the attached patent application and the equivalents of the patent application scope.