Method of making electronic materials

Manufacturing method of electronic materials

FIELD OF THE INVENTION The present invention relates to a method of texturing electronic materials, in which method involves forming a hard mask. In one embodiment, it involves converting a precursor into a top surface imaging layer in the direct patterning step.

BACKGROUND OF THE INVENTION Traditional methods are used in the semiconductor and packaging industries to form thin metal and metal oxide films in their products. Examples of such methods include evaporation, sputtering deposition or sputtering, chemical vapor deposition (CVD), and thermal oxidation methods. Evaporation is a method of heating the metal to be deposited near the substrate where it is desired to be deposited. Generally, it is carried out under vacuum conditions. The material to be deposited volatilizes and then condenses on the substrate to produce a covering layer, or a patternless film of the desired material, on the substrate. This method has several disadvantages, including the need to heat the material to be filmed to a high temperature and the need for high vacuum conditions. Unless a shield or mask is used during the evaporation process, this method will result in an unpatterned cover film.

Sputtering is a technique similar to evaporation, in which the material used for deposition is transformed into the gas phase by bombarding the material for deposition with incident atoms with sufficient kinetic energy, so that the particles of the material are expelled into the gas phase and then on the substrate Cohesion. Sputtering has the same disadvantages as evaporation. In addition, it also requires equipment and consumables that can generate incident particles with sufficient kinetic energy to expel the particles of these deposited materials.

CVD is similar to evaporation and sputtering, but it also requires that the particles deposited on the substrate undergo a chemical reaction during the deposition process to form a film on the substrate. Although CVD is different from evaporation and sputtering in that a chemical reaction is required, the CVD method still requires complicated equipment and harsh conditions of temperature and pressure during the film deposition process.

Thermal oxidation also requires harsh conditions of temperature and oxygen atmosphere. In this technique, an oxide film covering layer is produced on the substrate by oxidizing the unoxidized layer deposited on the substrate earlier.

There are several existing film deposition methods that can be performed at ambient temperature and pressure, including sol-gel methods and other spinning methods. In these methods, a solution containing a precursor particle is coated on the substrate, and these particles can then be converted into the desired film composition. The solution can be coated by spin coating or spin injection. At this time, the substrate is rotated around an axis and the solution is dropped into the middle of the substrate. After performing such coating, the coated substrate is subjected to high temperature treatment, thus converting the precursor film into a film of the desired material. Therefore, these methods do not allow direct imaging to form patterns of amorphous films. Instead, they will produce an unpatterned cover film formed from the desired material. Compared with the gas phase method, these methods have less stringent requirements on the equipment, but still have requirements on the external temperature to affect the conversion of the deposited film to the required material.

In a method of patterning the cover film, a photosensitive coating is applied to the cover film (generally, spin coating or other solution-based coating methods are used, or a dry photosensitive film is applied). The photosensitive layer is selectively exposed with light of a specific wavelength through the mask. Exposure changes the solubility of the exposed areas of the photosensitive layer, enabling the selective removal of exposed or unexposed areas with a developing solution. The remaining material is then used as a pattern transfer medium, or a mask for an etching medium, which forms a pattern on the required material. After this etching step, the remaining material (the former photosensitive material) is removed, and if necessary, all by-products generated during the etching method are cleaned away.

In another method of forming a patterned film on a substrate, a photosensitive material may be patterned as described above. After the pattern is formed, a conformal coating layer of the desired material can be deposited on the surface of the patterned material (previously photosensitive material), and then the substrate with the patterned material and the desired material covering film can be deposited Exposure to corrode the former photosensitive material. This treatment removes the remaining original photosensitive material, and together with it also removes a part of the cover film of the desired material on the surface. In this way, a patterned film of the desired material is obtained. In this "liftoff" method, an etching step is not necessary. However, it is still necessary to use an intermediate pattern transfer medium (photosensitive material), which is the disadvantage of this method. It is known that the "peeling" method has strict limits on the resolution (minimum size), which can be determined by the pattern of the required material. This shortcoming strictly limits the usefulness of this method.

Therefore, it is obvious that the cover film that needs to be patterned after deposition requires several extremely expensive and difficult processing steps.

In another method of forming a patterned film, a cover film of a desired material may be deposited on a substrate that has been patterned in advance by the aforementioned etching method, for example, by one of the above-mentioned methods. The covering film deposited in this way makes its thickness full and completely covers the existing pattern on the substrate. Then, a part of the cover film is removed in an isotropic manner until the remaining required material is at the same height as the surface of the patterned substrate. Therefore, the required material is present in the pattern embedded in the pre-patterned substrate. An etching method can be used to achieve isotropic removal of the required materials; generally, in the case of manufacturing semiconductor devices, this removal is achieved by a known method, such as chemical mechanical planarization (CMP). This involves the use of particle slurry with chemical reagents, through the combination of chemical and mechanical action, to remove a sufficient amount of the required material, embedded in the patterned substrate at the required position, leaving the required material . This method of forming a patterned film requires expensive and complicated planarization equipment and additional consumable materials, including planarized mats, slurries, and chemical reagents. In addition, the use of small particles of the slurry requires that these particles be removed from the planarized surface later, which also requires additional processing steps.

Although some of these methods have higher requirements for equipment than others, and the method of using a solution or a gas phase is different, for the formation of metal films and metal oxide films, such traditional processes are both different. It is not the best method, because for example, each of them requires expensive equipment, time-consuming operation, high temperature to achieve the desired result, and the obtained cover film is not patterned. If a pattern is required, another one is required. Pattern steps. Many of these methods have additional disadvantages. In many cases, polycrystalline films are formed. For many applications, such films are not suitable. Another promising solution of these methods is to use a precursor material, which can be coated on a substrate and selectively form images and patterns, and an amorphous film can be formed without intermediate steps.

One use of the film in semiconductor processing is to form a thin top surface imaging layer (hereinafter referred to as TSI), which is generally an organic surface layer that has been coated on a substrate. In this case, the organic layer need not be photoactive, because the film to be deposited is then patterned by conventional methods. For TSI, the use of such a film to give the processing method has several advantages, including the ability to provide plasma etching resistance without a photoresist mask, and the use of a thin film to provide increased lithographic resolution. rate. For TSI typical films including nitrides and oxides of metals and silicon, many studies have been conducted on a method known as silylation. This method involves depositing a silicon-containing compound film on the surface of a pre-deposited organic layer. Then, an image can be formed on the silicon-containing compound film to form a silicon oxide film. When the underlying organic layer is patterned by oxygen-plasma etching, it can be used as a TSI layer. Due to method and cost constraints, the acceptance of silylation by the semiconductor and packaging industries is irrelevant.

Another application of films in semiconductor processing is the formation of hard masks, such as in ion implantation methods. Ion implantation is a well-known technique used, such as forming doped regions on a substrate in semiconductor texture. Ion implantation often requires a patterned barrier layer, which is known as a hard mask, which directs the ions to be implanted to only a predetermined area. For example, in the first embodiment of US5,436,176 by Shimizu et al., a technique of performing maskless implantation on a silicon substrate covered with a silicon oxide film is disclosed, and it is disclosed that three implantations are performed with boron atoms. In addition, the same patent discloses a method of implanting using multiple hard masks in the triple repetition method in the third embodiment. This method sequentially includes the following steps: forming a mask on a silicon substrate covered by a silicon oxide film, and using a phosphorus-containing compound Perform implantation, form a second mask, implant with boron, and finally perform annealing.

As previously discussed, forming a hard mask using any of these methods requires a relatively large number of processing steps. It would be beneficial to eliminate certain steps before etching or ion implantation, because it would, for example, simplify the method used, increase its efficiency and reduce its cost.

One solution to this problem involves using photoresist as a mask. However, it is well known that the resistance of photoresist to certain plasma etching chemicals, especially when used for patterning organic layers, is very low. This organic layer can be used as an intermediate protective layer or as a low Dielectric materials with a dielectric constant (low K value) and low ion termination energy have found more and more uses. Therefore, an unacceptably thick mask is required to complete the etching of the layer to be patterned before the masking layer is completely etched away, or to avoid implanting the masked area on the substrate. Another disadvantage is that the ion-implanted photoresist is very difficult to remove from the wafer. I have also tried to solve this problem in other ways, such as coating a hard mask first, and then coating a photoresist layer on top of the hard mask, and then forming the upper pattern before etching or ion implantation. . Before plasma etching or ion implantation, combining some of the multiple steps disclosed in the prior art methods, or even eliminating one or more of them, will help simplify these methods. Therefore, a method that eliminates certain steps in the plasma patterning or ion implantation method will be very desirable.

As an inexpensive method of manufacturing metal and metal oxide hard masks, the present method for the deposition of metal complex precursors has been developed. An embodiment of this method, the photochemical metal-organic compound deposition method, involves the use of metal-organic compounds for metal complex precursors, as well as a method of converting metal-organic compounds into metal or metal oxide films, such as incident Radiation or heat. Specifically, in this method, for example, by dissolving the metal organic compound precursor in a suitable organic solvent to form a precursor solution, and depositing it on the surface by any known method, the metal organic compound precursor is coated. Cloth on the surface. Then through partial conversion methods and/or conversion methods, such as energy sources, such as exposure under light, ion beam bombardment, electron beam bombardment, or exposure under heat treatment or annealing, the precursor is at least partially converted into a metal or metal oxide layer . Therefore, the method has applications in, for example, the semiconductor and packaging industries.

Hill et al. US5,534,312 discloses a method of fabricating patterned metal-containing materials on a substrate without using a photoresist. The method includes depositing an amorphous film of a metal complex on the surface of the substrate. Place it in a selected atmosphere and use electromagnetic radiation, preferably ultraviolet light, optionally through a mask, to expose the selected area of the film to cause the metal complex in the selected area to undergo photochemical reactions and other steps. However, this reference material does not envisage using a patterned metal-containing material as a hard mask to protect the bottom layer from the plasma etching environment.

US 6,071,676 to Thomson et al. discloses that the manufacturing method of its integrated circuit causes degradation of the coated compound when the compound is in contact with radiation or ion beam. In other words, the size of the deposited layer where the degradation of the compound occurs is proportional to the focal width of the radiation beam. According to the public, this method can reach the nanometer scale. Where the compound degrades, a deposited layer of metal or other conductive material is formed, and this method can then be used to directly manufacture integrated circuits on the substrate. It is said that the deposited layer is preferably a metal or a metal alloy. The metal can be gold, tin or chromium, or the deposited layer can be a non-metal or semi-metal conductor, such as germanium. In another aspect, a method for manufacturing an integrated circuit is provided. The method includes coating a substrate that will degrade under the action of radiation or ion beams to obtain a conductor, preferably a metal deposition layer, and a compound Select the surface area to be irradiated with radiation or ion beams, and to remove degraded and unaffected compounds from the substrate.

The method of the present invention can provide a patterned hard mask to replace the oxide layer and photoresist layer used in the traditional TSI method and ion implantation method, and simplify these methods by reducing the number of processing steps that must be performed. Another advantage of the present invention is that the obtained material has better resistance to plasma etching chemicals. This also gives the present invention another advantage, which is that it allows the use of extremely thin films as masks, improves the final resolution of the lithographic printing method, and can form a smaller and finer printing appearance. Another advantage of the present invention is that the obtained material has better ion implantation barrier performance and termination energy. In addition, the method of the present invention is advantageous in that it enables new materials to be used to form patterned layers, such as platinum, iridium, iridium oxide, ruthenium, and ruthenium oxide. These materials are known to be very useful in the prior art. It is difficult or impossible to etch by traditional methods.

SUMMARY OF THE INVENTION One embodiment of the present invention is a method of forming a hard mask on a substrate, which includes the following steps:-selecting at least one precursor material;-forming a layer containing the precursor on the top of the substrate; -Covering at least a part of the precursor layer;-developing the precursor layer, thereby forming a pattern on the precursor layer; and-transferring the pattern to the substrate, so that photoresist is not used when forming the pattern.

The unconverted part of the precursor layer can be developed and removed with a developer. In addition, a developer can also be used to develop and remove the converted part of the precursor layer. The developer may be a liquid developer containing at least one alcohol and at least one ketone, wherein the total volume of all alcohols is greater than 50% of the total volume of all alcohols and all ketones present in the liquid developer. The at least one alcohol of the developer is preferably isopropanol, and the at least one ketone is preferably methyl isobutyl ketone. The volume ratio of isopropyl alcohol and methyl isobutyl ketone is greater than about 1:1 and less than about 40: 1.

Another embodiment of the present invention is a method of forming a hard mask on a substrate. The method includes the following steps:-selecting at least one precursor material;-optionally forming a protective layer on top of the substrate; A layer containing an unconverted precursor is formed on the protective layer;-at least part of the unconverted precursor layer is partially converted;-at least part of the unconverted precursor layer is substantially removed to form a pattern; and-at least a part of the partially converted precursor is formed The body layer is transformed to form a hard mask.

An energy source selected from light, electron beam irradiation, ion beam irradiation, and a combination thereof may be used to achieve partial conversion through a patterned mask including at least a portion of the energy source that is substantially transparent. The use of a developer can substantially remove at least part of the uncovered precursor layer. The conversion can be achieved with energy sources selected from light, electron beam irradiation, ion beam irradiation, thermal annealing, and combinations thereof.

Another embodiment of the present invention is a method of forming an etching pattern on a substrate, the method comprising the following steps:-selecting at least one precursor material;-forming a layer containing an unconverted precursor on the top of the substrate; -At least part of the unconverted precursor layer is partially converted;-at least a part of the unconverted precursor layer is substantially removed;-by converting at least a part of the partially converted precursor layer to form a hard mask; and-by engraving Etching at least part of the substrate substantially covered by the hard mask to form at least one patterned area on the substrate.

Another embodiment of the present invention is a method of forming a patterned thin top surface, the method comprising the steps of:-selecting at least one precursor material containing a metal complex;-forming a pattern transfer layer on top of the substrate;- A layer containing the unconverted precursor is formed on top of the pattern transfer layer;-a portion of the unconverted precursor layer is exposed through a patterned mask including at least a portion that is substantially transparent to light, thereby performing the exposed portion Conversion;-Substantially remove at least a part of the unconverted precursor layer, thereby removing at least a part of the coverage of the pattern transfer layer;-Form a hard mask by converting at least a part of the partially converted precursor layer;-At least partially converted The uncovered part of the precursor and the pattern transfer layer is etched, thereby forming at least one etched part from the uncovered pattern transfer layer; and-substantially removing the remaining at least partially converted precursor layer and the pattern transfer layer , Thereby exposing at least a part of the substrate.

The pattern transfer layer can be selected from photoresist, polyimide, polymethyl methacrylate, novolac resin and epoxy resin.

Another embodiment of the present invention is a method of forming a patterned thin top surface on a lift-off layer. The method includes the following steps:-selecting at least one precursor material containing a metal complex;-forming one on top of the substrate Isolation layer layer);-a lift-off layer is formed on top of the isolation layer;-a layer containing unconverted precursor is formed on top of the lift-off layer;-part of the unconverted precursor layer is exposed through a pattern mask , This mask includes at least a portion that is substantially transparent to light, thereby partially converting the exposed portion;-substantially removing at least a portion of the unconverted precursor layer, thereby exposing at least a portion of the lift-off layer, and the rest The lift-off layer is covered by the partially converted precursor layer;-at least a part of the partially converted precursor layer is converted to form a hard mask;-the at least partially converted precursor and the exposed portion of the lift-off layer are subjected to various An anisotropic removal step (mean), thereby substantially removing the exposed part of the lift-off layer and at least a part of the isolation layer under the exposed part of the lift-off layer, exposing at least a part of the substrate;-the at least partially converted precursor is lifted The covering portion of the layer and at least a portion of the isolation layer under the covering portion of the lift-off layer are subjected to an isotropic removal method (mean);-a metal film is deposited on top of at least a portion of the exposed substrate and on the top of the at least partially converted precursor; -Substantially removing the metal on top of the at least partially converted precursor; and-substantially removing the remaining at least partially converted precursor, lift-off layer and isolation layer, thereby forming a metal pattern on top of the substrate.

Another embodiment of the present invention is a method of forming a patterned thin top surface on the lift-off layer, the method includes the following steps:-selecting at least one precursor material containing a metal complex;-forming on top of the substrate A layer containing an unconverted precursor material;-at least a part of the unconverted precursor layer is partially converted;-at least a part of the unconverted precursor layer is substantially removed, thereby forming a taper inward in the part of the partially converted precursor The sidewall profile and expose at least a part of the substrate;-forming a hard mask by converting at least a part of the partially converted precursor layer;-depositing a metal film on at least a part of the exposed substrate and on top of the at least partially converted precursor;

-Substantially removing the metal on top of the at least partially converted precursor; and-substantially removing the remaining at least partially converted precursor, thereby forming a pattern of metal on top of the substrate.

Another embodiment of the present invention is a method of forming an injection zone on a substrate, the method comprising the following steps:-selecting at least one precursor material;-optionally forming a protective layer on top of the substrate;-here A layer containing at least one unconverted precursor material is formed on top of the protective layer;-by partially converting at least a part of the unconverted precursor layer to form a part of the partially converted precursor layer;-by using a developer, basically Removing at least a part of the unconverted precursor layer;-forming a hard mask by converting at least a part of the partially converted precursor layer;-implanting ions on at least a part of the substrate that is not substantially covered by the hard mask, on the substrate At least one injection zone is formed.

Energy sources selected from light, electron beam irradiation, ion beam irradiation, and combinations thereof can be used to achieve partial conversion by including at least one patterned mask that is transparent to these energy sources. The conversion can be achieved with energy sources selected from light, electron beam irradiation, ion beam irradiation, thermal annealing, and combinations thereof. Ion implantation can be performed by exposing the uncovered substrate to an ion beam.

Another embodiment of the present invention is to form a double corrugated structure in a dielectric layer (damascene architecture), this method includes the following steps:-selecting at least one precursor material;-forming a dielectric layer with a characteristic thickness on top of the substrate;-forming a dielectric layer containing a first unconverted layer on top of the dielectric layer The precursor layer;-using a first partial conversion method (mean) on at least a portion of the unconverted first precursor layer to form a partially converted first precursor layer portion;-using the first removal method to substantially remove at least a portion of the first precursor layer The unconverted precursor layer exposes at least a portion of the dielectric layer to form a first pattern that is not covered by the at least partially converted first precursor layer;-using the first conversion method on at least a portion of the partially converted first precursor layer, Forming a hard mask;-forming a rotating planarization layer on top of the exposed portion of the dielectric layer and on top of the at least partially converted first precursor layer;-forming a second unconverted layer on top of the rotating planarizing layer A layer of the precursor;-by using a second partial conversion method on at least a portion of the second unconverted precursor layer to form a partially converted second precursor layer;-by using a second removal method, substantially removing at least a portion of the first precursor layer 2. Unconverted precursor layer, exposing at least a part of the rotational planarization layer to form a second precursor layer that has not been at least partially converted to cover the second pattern;-by using a second pattern for at least a part of the partially converted second precursor layer A conversion method to form a hard mask;-at least a portion of the dielectric layer and the rotational planarization layer underneath that are not substantially covered by the second hard mask are used for the first etching method to form at least one in the dielectric layer The patterned area allows the first etching method to remove a layer of dielectric layer smaller than the thickness in the depth direction;-by using the third removal method, the remaining at least part of the unconverted second precursor layer is basically removed and rotated planarization Layer, thereby exposing the at least partially converted first precursor layer;-forming at least one layer in the dielectric layer by using a second etching method on at least a portion of the dielectric layer that is not substantially covered by the first hard mask In the first pattern area, in the first pattern area, a portion smaller than the thickness of the dielectric layer is removed in the depth direction of the dielectric layer by the second etching method; and in the second pattern area, the second etching method is basically used. The entire thickness of the dielectric layer is removed in the depth direction, thereby removing at least a portion of the substrate from the cover, and-optionally, by using a fourth removal method, substantially removing the remaining at least partially converted first precursor layer.

The dielectric layer is preferably a dielectric material with a low dielectric constant. At least one of the first and second etching methods is preferably an anisotropic plasma containing oxygen.

In each of these embodiments, the preferred precursor material is a metal complex containing at least one ligand and at least one metal selected from the group consisting of acetylacetonate, carboxylate, alkoxy Group, azide group, carbonyl group, nitrate group, amine, halogen group, nitro group and their mixture; and the metal is selected from Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn , Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au , Pb, Th, U, Sb, As, Ce, Mg and their mixtures.

Brief Description of the Drawings Figure 1 is a method flow chart that regards the steps of the method as variables of the method; Figure 2 illustrates the basic sequence of the steps in an embodiment of the method of the present invention; Figure 3 illustrates the prior art manufacturing The method and the use of the hard mask used in the semiconductor connector; Figure 4 illustrates the manufacturing method according to the present invention and the use of the hard mask; Figure 5 illustrates the prior art of patterning with TSI; Figure 6 illustrates the use of the hard mask according to the present invention The manufacturing method and the use of the TSI layer; FIG. 7 illustrates the prior art method of implementing the layer peeling method; FIG. 8 illustrates the method of implementing the layer peeling according to the present invention; FIG. 9 illustrates another method of implementing the layer peeling according to the present invention; FIG. 10 Description of the prior art method for the integration of the dual-corrugation method; FIG. 11 illustrates the method for the integration of the dual-corrugation method according to the present invention, which has fewer steps than the method of FIG. 10; And using the prior art method of ion implantation; Figure 13 illustrates the prior art method of manufacturing an ion implantation hard mask and using it for ion implantation according to an embodiment of the present invention; Figure 14 shows the formation of two different precursors ZrO2 film shows different refractive index performance; Figure 15 shows the refractive index of different ZrO2 formed by thermal conversion and photochemical conversion; Figure 16 describes the stripes caused by the use of special solvents after coating the precursor solution on the substrate; Figure 17 shows The thermal contrast curve for BST; Figure 18 shows the photochemical contrast curve for BST; Figure 19 shows the thermal/photochemical combination contrast curve for BST; Figure 20 is a graph of the thickness of the novolak resin versus the etching time; Figure 21 is for The thickness of fully converted PZT and TiO2 vs. etching time.

Detailed description of the invention This method takes into account advantages that are not possible with other film deposition and manufacturing methods. As a result, the user has a stronger ability to control and manipulate the resulting film to adapt it to the desired application. Therefore, this method can be used in a wide range of applications.

The present invention provides a method of manufacturing a patterned film of a desired material. It is important to recognize the difference between an amorphous film and a polycrystalline film and a crystalline film. At the same time, it is necessary to recognize the difference between an amorphous film and a more ordered film. In addition, it is also necessary to recognize the amorphous film obtained by different film forming methods. The membranes are different from each other. In addition, the different properties of different amorphous films formed by different methods can be controlled, and will result in special chemical, physical and mechanical properties that can be used in specific applications, such as semiconductor devices and/or various types of Floor. The hard mask formed by the present method including at least one step of converting such an amorphous film is preferably patterned and therefore can be used to transfer the pattern to a substrate. Hard masks include, but are not limited to, implantation masks, etching masks, and pattern transfer layers or masks, such as lift-off masks.

An advantage of this embodiment of the method is that it does not need to use traditional patterning materials, that is, photoresist, to produce patterned electronic materials when forming patterns. Another advantage of this method is that the amorphous film of the precursor material that can be formed can optionally be patterned directly on the substrate without using an intermediate patterning material. As a result of understanding the embodiments of the present invention, important and unique properties can be obtained, although this deposition method does not use other deposition and film formation methods. Figure 1 provides an overview of the method with a flow chart. This flow chart shows the various steps as an example. These successive steps are used to obtain the desired material film with the best performance for the specific application. Many of these steps can be arbitrarily selected according to the final application of the membrane. The present invention is not limited to these steps, and other steps may be included according to the end use of the film. Professionals in the field will know which steps should be included and which should not be included in order to achieve the desired results for a particular application.

There are different options in each step, and the operation of these options will have an impact on the film obtained. For example, in step 1 of Figure 1, the selection scheme can include the composition of the precursor material, the solvent used in the precursor material, regardless of whether the solvent is used in the precursor material, and the additives that can be used in the precursor material And/or a rate enhancer that can be included in the precursor material.

In step 2 of FIG. 1, the options may include cleaning of the substrate, deposition of a barrier layer, deposition of an adhesion promoter, and/or use of an active layer.

In step 3 of FIG. 1, the selection scheme may include the method of coating the precursor film, the atmosphere and/or the deposition temperature when the precursor is coated.

In step 4 of FIG. 1, the options may include heat treatment, treatment with electron beams, treatment with ion beams, treatment with microwaves, and/or use of special atmospheres.

In step 5 of FIG. 1, the options may include whether the film is covered, exposed or patterned, or mixed with each other, and/or a specific atmosphere is used.

In step 6 of FIG. 1, the options may include thermal annealing, microwave treatment, electron beam treatment, ion beam treatment, electroplating, and/or use of a specific atmosphere.

In step 7 of FIG. 1, the selection scheme may include whether to use a wet technique or a dry technique to form the pattern.

In step 8 of FIG. 1, the selection scheme may include annealing and/or using a specific atmosphere. In this step, any amorphous film formed can also be converted into a polycrystalline or crystalline film by applying high temperature or various other nucleation techniques, such as light-induced nucleation, and for some applications, this may be a particularly desirable A step of.

These options are exemplary in nature and are not an exhaustive list of options that can be manipulated to affect the performance of the resulting membrane. The specific features and embodiments of the present invention will be described in detail below.

When a patterned film is required, the method described here can be carried out in a photochemical manner. It does not require an intermediate patterning material, such as photoresist. It can be carried out under ambient conditions or under other conditions. For example, in an atmosphere of air or other composition and/or under different pressures, such as ambient pressure, above or below ambient pressure, other processing steps can be combined to produce unique materials, layers and structures.

When this method is implemented in the light decomposition method, this method is basically implemented at ambient temperature, while other prior art methods require the use of high temperature for pattern transfer, which is often higher than 100°C. From a manufacturing point of view, this limitation imposes strict processing constraints and restricts the selection of materials used in the assembly of devices related to these methods.

Under substantially ambient pressure, the method of the present invention generally performs satisfactorily. On the contrary, in addition to the above-mentioned limitations, many prior art deposition methods must be performed under high vacuum, using expensive and complicated equipment that is difficult to operate and maintain.

The method of the present invention makes it easy to form a thin layer from the precursor material on the substrate. The precursor contains specially designed molecules that enable it to be uniformly coated on the substrate, and the resulting film has high optical properties. In the case of this method, it has high light sensitivity. The characteristics of the precursor molecules are very different-a variety of metal complexes with the general formula MaLb, containing at least one metal (M) and at least one or several appropriate ligands (L), namely Both a and b are integers of at least 1, and such metal complexes are contemplated by the present invention.

If multiple metals are used, all the metal atoms may be the same, or not all of the same atom and/or have different valences, such as BaNaFe(II)Fe(III), or some of them are the same, while others are Different atoms and/or have different valences, such as Ba2Fe(II)Fe(III). In any case, the metal M may be an alkali metal or alkaline earth metal, such as Ba or Li, a transition metal such as Cr or Ni, a main group metal such as Al or Sn, or an actinide element, such as U or Th. Preferably, each metal is independently selected from Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, and Mg.

If multiple ligands are used, all the ligands can be the same or different, or some of the ligands are the same, while others are different. In any case, the ligand should be selected so that a substantially unconverted precursor complex can be formed, and has the following properties: 1) It can be deposited on the substrate in an amorphous form; 2) Amorphous film Is stable, or at least metastable; 3) When absorbing energy, such as photons of the required energy, the film can be transformed into different metal-containing materials through a chemical reaction, and 4) Any energy-induced chemical The by-products of the reaction should be removable, that is, they should be sufficiently volatile to be able to be removed from the membrane.

In order to obtain the first two of these results, the complex should have low polarity and low intermolecular force. Since organic groups generally have low intermolecular forces, ligands with organic groups on their periphery tend to meet the first two requirements. If the absorbed energy is light, the chemical reaction in step (3) is known to be a light-induced reaction.

The deposited film of the substantially unconverted precursor is amorphous, or at least substantially amorphous. Therefore, in order to produce a metal complex that hinders crystallization, the ligand L preferably makes the complex asymmetric. The use of ligands that have two or more stereoisomeric forms can make the complex asymmetric. For example, if L is racemic 2-ethylhexanoate, the resulting metal complex is asymmetric because the complex has several different stereoisomeric forms. The size and shape of the organic part of the ligand can be selected to optimize the stability of the film and adjust the thickness of the film deposited by the selected film deposition method.

By manufacturing a complex film with several different ligands attached to each metal atom, the stability of the amorphous film to crystallization can also be enhanced. Such metal complexes have several isomer forms. For example, the reaction of CH3HNCH2NHCH3 with a mixture of nickel salt (II) and KNCS results in a mixture of various isomers. It is known that the chemical properties of different isomers are significantly different, and the presence of several isomers in the membrane weakens the ability of the complex to crystallize in the membrane.

The complex must be stable, or at least metastable, meaning that under the conditions of this method, the complex will not decompose rapidly and spontaneously. The stability for a given metal complex may depend, for example, on the oxidation state of the metal in the complex. For example, it is known that Ni(O) complexes are unstable in air, while Ni(II) complexes are stable in air. Therefore, the method for depositing Ni-based films that includes a processing step in the air should include Ni(II) complexes that are superior to Ni(O) complexes.

Partial conversion and conversion are caused by chemical reactions in the membrane, which will turn part of the conversion zone or conversion zone into the desired conversion material. In an ideal manner, at least one ligand reacts with the complex and is connected by a bond, and the bond is cleaved when the complex is affected by the partial conversion method and/or the conversion method to produce an excited state. In a photochemical reaction initiated by light, more preferably ultraviolet light, as a partial conversion method and/or conversion method, it is preferable to cleave the active group from the complex. In order to make such a photochemical step in the method more effective, it is particularly preferable that the intermediate product is generated when the active group is cut and becomes unstable and spontaneously transforms into the desired new material and volatile by-product.

There are several mechanisms by which appropriate photochemical reactions can occur. Examples of suitable reaction mechanisms that can be operated alone or in combination according to the present invention are as follows: (a) Absorption of photons can place the complex in an excited state of ligand-metal charge transfer. In this state, the metal in the metal complex -The ligand bond is unstable, the bond is broken and the remaining part of the complex decomposes spontaneously; (b) Absorbing photons can place the complex in a metal-ligand charge transfer excited state, in this state, complex The metal-ligand bond in the compound is unstable, the bond breaks back, and the remaining part of the complex decomposes spontaneously; (c) the absorption of photons can place the complex in the dd excited state, in this state, The metal-ligand bond in the complex is unstable, the bond is broken and the remaining part of the complex decomposes spontaneously; (d) Absorption of photons can place the complex in an excited state of charge transfer in the molecule, in this state , The metal-ligand bond in the complex is unstable, and the bond breaks and the remaining part of the complex decomposes spontaneously; (e) absorption of photons can place at least one ligand of the complex in the local coordination In the excited state, the bond between the excited ligand and the complex is unstable, and the bond is broken and the remaining part of the complex decomposes spontaneously; (f) Absorption of photons can place the complex in the molecule for charge transfer excitation State, so that at least one ligand of the complex is unstable and decomposes, and then the remaining part of the complex is unstable and decomposes spontaneously; (g) absorption of photons can decompose at least one of the complex The ligand is placed in a localized ligand excited state, where the excited ligand is unstable and decomposes, and then the remaining part of the complex is unstable and decomposes spontaneously; and (h ) Absorption of photons can place the complex in a metal-ligand charge transfer excited state. In this state, at least one ligand of the complex is unstable and decomposes, and then the rest of the complex It is unstable and decomposes spontaneously. However, in the broad characteristics of the present invention, the composition of the present invention is not limited to these reaction mechanisms.

As an example, metal complexes and their metal and ligand components are described in US 5,534,312, which is incorporated herein by reference in its entirety. Preferred metal complex precursors include various ligands that meet the above criteria. More preferred ligands are selected from acetylacetonates (also known as acac or 2,4-pentanedione) and their anions, substituted acetylacetonates, namely:And its anion, acetonyl acetone (known also as 2,5-hexanedione) and its anion, substituted acetonyl acetone, namely:And its anion, dialkyl dithiocarbamate, namely:And its anion, carboxylic acid, namely:For example, caproic acid, where R=CH3(CH2)4, carboxylate, namely:For example, caproate, where R=CH3(CH2)4, pyridine and/or substituted pyridine, namely:Azide compounds, namely N3-, amines, namely RNH2, diamines, such as H2NRNH2, arsine, namely:Arsenic, namely:Phosphine, namely:Diphosphine, namely:Aromatics, namely:Hydroxyl, namely OH-, alkoxy ligands such as RO-, ligands such as (C2H5)2NCH2CH2O-, alkyl ligands such as R-, aryl ligands and their mixtures, where each R, R', R", R'" and R"" are independently selected from organic groups, preferably independently selected from alkyl, alkenyl, aralkyl, and aralkenyl.

As used herein, the term "alkyl" refers to a straight or branched hydrocarbon chain. As used herein, straight or branched hydrocarbon chain means any substituted or unsubstituted acyclic carbon-containing compound, including alkanes, alkenes and alkynes. Examples of alkyl groups include lower alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or isohexyl; higher alkyl groups, such as n-heptyl, octyl , Isooctyl, nonyl, decyl, etc. Lower olefins such as ethylene, propylene, propyne, butene, butadiene, pentene, n-hexene or isohexene; and higher olefins such as n-heptene, n-octene, isooctene, nonene, decene and the like. The general practitioner is familiar with many linear, i.e. linear and branched alkyl groups, all of which are within the scope of the present invention. In addition, such alkyl groups also contain various substituents, in which one or several hydrogen atoms are replaced by functional groups or in-chain functional groups.

As used herein, the term "alkenyl" refers to a straight or branched hydrocarbon chain in which at least one carbon-carbon bond is a carbon-carbon double bond. As used herein, the term "aralkyl" refers to an alkyl group whose end is substituted with at least one aryl group, such as a benzyl group. As used herein, the term "aralkenyl" refers to an alkenyl group whose end is substituted with at least one aryl group. As used herein, the term "aryl" refers to a cyclic hydrocarbon having a conjugated double bond system, often including at least 6 π electrons. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anisyl, tolyl, xylyl and the like.

As understood by those skilled in the relevant fields, in the text of the present invention, the term "functional group" generally refers to a part having intra-chain, side bond, and/or terminal functional groups. Examples of functional groups in the chain include esters, ethers, amides, carbamates, and their thio derivatives, in which at least one oxygen atom is replaced by a sulfur atom. As examples of side bonds and/or terminal functional groups, halogens, such as fluorine and chlorine, and hydrogen-containing groups such as hydroxyl, amino, carboxyl, mercapto and amide, isocyanate, cyano, epoxy and alkene groups can be cited. Bonded unsaturated groups, such as allyl, acryl, and methacryl, and maleate and maleimide groups.

In order to enhance the required photochemical properties, including the tendency of photochemical reaction products to decompose by themselves, a ligand containing and/or one or several groups selected from the following can be used alone or together with the ligands listed above: Oxo, namely O2-, oxalate, namely:Halide, hydrogen, hydride, that is H-, dihydride, that is H2, hydroxyl, cyano, that is CN-, carbonyl, nitro, that is NO2, nitrite, that is NO2-, nitrate, that is NO3- , Nitroso groups, namely NO, ethylene, acetylene, that is RR' thiocyanate, that is SCN-, isothiocyanate, that is NCS-, hydrated, that is H2O, azide, carbonate, that is CO3-2 Amine and thiocarbonyl, where each R and R'are independently selected from organic groups, preferably independently selected from alkyl, alkenyl, aralkyl and aralkenyl. Each ligand is even more preferably selected from acetylacetonate, carboxylate, alkoxy, oxalate, azide, carbonyl, nitro, nitrate, amine, hydrogen and their anions.

Preferably, the metal complex precursor is selected from complexes containing at least one ligand and at least one metal, wherein the ligand is selected from acetylacetonate, carboxylate, alkoxy, azide, carbonyl, Nitrate, amine, halogen, nitro and their mixture; wherein the metal is selected from Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg and their mixtures.

The precursor can be directly coated on the substrate. Also preferably, the precursor can be dissolved in one or several solvents to form a precursor solution. In this way, it can be easily applied to the substrate by various methods known to those skilled in the art, such as spin-coating or spraying the solution onto the substrate. The solvent can be selected based on several criteria alone or in combination, including the ability of the solvent to dissolve the precursor, the inertness of the solvent to the precursor, the viscosity of the solvent, the solubility of oxygen or other environments or other gases in the solvent, the ultraviolet light of the solvent, Visible light and/or infrared absorption spectrum, absorption cross section of the solvent relative to the electron beam and/or ion beam, the volatility of the solvent, the diffusion ability of the solvent through the subsequently formed film, the purity of the solvent relative to the different solvent isomers that exist , The purity of the solvent relative to the existing metal ions, the thermal stability of the solvent, the ability of the solvent to affect defects or nucleation points in the subsequently formed film, and environmental considerations involving the solvent. Examples of solvents include alkanes such as hexane, ketones such as methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK), and propylene glycol but methyl ether acetate (PGMEA).

The concentration of the precursor in the solution can be varied within a wide range, and can be selected by professionals in the field through as few routine experiments as possible, so as to include its thickness and/or sensitivity to light or particle beam irradiation. The performance of the precursor film meets the desired application.

However, the selection of the precursor may have a significant impact on the performance of the desired film, which is not easy for those skilled in the art to predict. For example, two precursors ML and ML', each composed of a metal M and one of two different sets of ligands L or L', are expected to form a film of the same desired material because, for example, the precursor In the process of transforming the body into a hard mask, the part of the ligands that are different from each other will be removed. In fact, these two similar reagents assume that the same membrane product may have significant differences in its performance. Examples of properties that may be affected in this method include dielectric constant and the presence/absence of any secondary or tertiary structure in the film. Possible reasons for this difference can be related to the rate of formation of the amorphous material and the ability of the light to expel the ligand to remove energy from the photogenerated film of the desired material. The presence of ligand fragments during the exposure process can affect the method of film formation, and affect phenomena such as film diffusion, nucleation, and crystal growth.

Furthermore, the selection of precursors during film formation and photochemical exposure may further affect the activity of the desired material film on the gas components of the atmosphere in which the desired film is formed. This may affect, for example, the oxidation rate of the deposited film, and depending on the desired product, either a high rate or a low rate may be an advantage. In addition, it is also recognized that the recovery ability of the film, that is, the ability to reduce cracks as much as possible, and the ability to shrink or densify, will be fundamentally affected by the selection of precursors, while professionals in the field will see different precursors. Experience produces the same result.

Optionally, chemical additives are present in the precursor or the precursor solution. This can be due to any one or several of the following reasons: controlling the light sensitivity of the subsequently deposited precursor or film, helping to deposit a uniform and defect-free film on the substrate, changing the viscosity of the solution, adding The high film formation speed helps to avoid film cracking during the subsequent exposure process, change other overall properties of the solution, and change the properties of the required material film in an important way. In addition to the criteria used in selecting the appropriate solvent, additives should be selected in accordance with these criteria. Preferably, the precursor or the precursor solution contains substantially no particle contamination to enhance its film-forming performance.

For this method, the nature of the substrate on which the precursor is to be coated is not critical, although this will affect the deposition method of the precursor film and the solvent used for deposition (if used). The substrate may include, but is not limited to, simple salts such as CaF2, semiconductor surfaces, including silicon, compound semiconductors, including silicon-germanium and III-V and II-VI semiconductors, printed and/or laminated circuit board substrates, metals, ceramics, and glass . Silicon wafers, ceramic substrates and printed circuit boards have been widely used. Before using them in this method, the substrate can be coated with a single-layer or multi-layer coating, such as a dielectric layer, photoresist, polyimide, metal oxide, thermal oxide, conductive material, insulating material, Ferroelectric materials or other materials used in the structure of electronic devices. When oxygen plasma is used for patterning and the precursor material is used as a TSI reagent, the bottom layer is suitably an organic material, including but not limited to novolac resin, polymethyl methacrylate (PMMA), polymethylpentene Diimide (PMGI), polyimide and poly(p-hydroxystyrene) (PHOST).

Once the hard mask is formed, the metal atoms in it will "bump" on the underlying substrate to a certain extent in the subsequent steps. This can be overcome by carefully selecting the formulation conditions and/or thickness of the precursor. In addition, an optional protective layer can be used between the substrate and the precursor layer. After the hard mask formation process is completed, it can still protect the substrate. Before coating the precursor or the precursor solution, at least one protective layer may be optionally coated on the substrate. The protective layer can be coated on the substrate by various methods known to those skilled in the art. When the method includes an ion implantation step, the protective layer is particularly desirable.

The preparation of the substrate before the deposition of the precursor film may have a significant impact on the final performance of the required hard mask. Therefore, for example, certain surface properties may be required, or vice versa, depending on the specific hard mask used. The preparation of the substrate may include a simple cleaning process to remove undesired substances from the surface of the substrate, and before the patterning step, deposition of barrier materials, deposition of adhesion promoting materials, or deposition of active materials for inducing deposition in the deposited material film Chemical changes, such as coupling agents.

The coating method of the precursor or the precursor solution can be selected according to the condition of the substrate and the intended application. Some examples of available coating methods known to those skilled in the art include spin coating, spray coating, drop coating and roll coating, imprinting, meniscus coating, and various ink printing methods, such as inkjet (inkjet- type) method. Various variables of the coating method can be selected to control the thickness and uniformity of the deposited film, minimize edge effects and reduce the formation of voids or pinholes in the film, and ensure that the precursor or precursor is consumed during the coating process The volume of the body solution is not more than necessary. Coating the precursor film with the best method will result in a very smooth film as desired.

The deposited film is optionally subjected to baking or vacuum steps, during which any solvent remaining in the deposited film can be driven off. Of course, if a baking step is used, it is important to keep the temperature of this step below the thermal decomposition temperature of the precursor molecules. The method of the present invention allows the precursor cast film to be thermally covered or heat-treated or annealed, so that it can be transformed into a uniform covering coating or film of the desired material by heat, which is converted into a partial transformation for pattern formation when the heat treatment is not used. And/or the converted dose may be less filmy. In this processing step, the deposited film may optionally be subjected to other treatments, including but not limited to overlaid photochemical exposure or electron beam exposure and microwave treatment.

It has been recognized that the baking step in this method step can help to drain the solvent from the precursor film and also cause the thermal decomposition process. Both of these mechanisms contribute to the overall effect of the method, leading to, for example, a reduction in the required dosage in the subsequent partial conversion and/or conversion step. It is further recognized that in such a baking step, a new material different from the deposited film or the film of the desired material can be formed. The effect may significantly change the future properties of the required material, including dielectric constant, nucleation properties, properties of forming material varieties, and crystallization properties, which are not easily foreseen by professionals in the field. For example, in some applications, it is preferable to use a two-component system, in which one material is activated in the pre-baking step, and another compound is selected to be activated by photochemical or high-energy thermal methods. Deposition from the precursor mixture will enable the efficient design of a system that has the advantage of the different chemical properties of the material formed by the baking and subsequent partial conversion and/or conversion steps.

The deposited film is then subjected to partial conversion and/or conversion, that is, the action of energy, so that the precursor is at least partially converted. The whole or selected parts of the deposited film can be exposed to the energy source. The energy source can be, for example, a light source of a special wavelength, a coherent light source of a special one or several wavelengths, a broadband light source and an electron beam (e-beam) source or an ion beam source. Light with a wavelength range of about 150 to about 600 nm is suitable for use. The preferred light wavelength is about 157 to about 436 nm.

In certain embodiments of the invention, the energy source is a light source oriented through an optical mask used to define an image on the surface. The mask consists of substantially transparent and substantially opaque or light-absorbing areas. The mask may also include optical enhancement features, such as phase shift technology. However, the energy does not have to be irradiated through the mask. For example, if it is not necessary to form a pattern on the material, a diffuse or covering type energy source can be used for exposure, and the exposure energy can be provided by a thermal energy source or a wide light beam.

The atmosphere and pressure (both total pressure and partial pressure) in which the deposited film undergoes at least partial conversion can be important process parameters. Generally speaking, it is suitable and economical to be an air atmosphere, but it may be preferable to change the composition of the atmosphere during at least partial conversion. One reason for this is that if short-wave light is used, the transmittance of exposure light can be increased, because air may weaken such light. Therefore, by changing the intensity of light, for example, increasing the light, a thermal reaction can be initiated in the film to produce a product film. It may also be desirable to change the composition of the atmosphere to change the composition or performance of the product film. For example, exposure to copper complexes in air or oxygen atmosphere can result in the production of copper oxide. By substantially removing oxygen from the atmosphere, a film mainly composed of reduced copper can be formed. For example, if the precursor to be converted must be a dielectric film, it is preferable to perform a partial conversion or conversion step in the presence of oxygen, or if the precursor to be converted must be a metal film, it is preferable to perform a partial conversion or conversion in the presence of a reducing gas, such as hydrogen. Conversion step. In addition, by changing the humidity in the atmosphere, the water content in the film can be changed.

The use of partial conversion steps or different sequential steps known as "substrate pretreatment" can be advantageous from a process flow point of view, for example in expensive equipment, such as steppers, in the substrate The time required for the exposure of the precursor on top is as short as possible.

After the deposited film is at least partially converted, the precursor film may optionally be treated by any of various methods known in the art, and then at least a portion of the unconverted precursor layer is removed. These methods include, but are not limited to, annealing treatments such as thermal annealing, laser annealing or plasma annealing steps, exposure to special atmospheres, such as oxidizing or reducing atmospheres, ion implantation, microwave treatment, and electron beam treatment. If the partially converted area can be used as a nucleation point for electroless plating of the unconverted area of the precursor, an optional electroplating step can be used in this step.

The unexposed area or part of the unexposed area of the deposited film can then be removed by using a removal method (or development). For example, the development method may include a development composition, which may be applied as a liquid or a solution in a puddle development or immersion wet development method. In addition, a dry development method similar to a dry patterning method conventionally used in the semiconductor industry can be used as a development method. Preferred removal methods include spray development, slurry development, and immersion wet development.

The formulation and/or use conditions of the developer should be such that there is a difference in solubility between the exposed and unexposed areas of the film. This difference in solubility is used to remove preferably selected areas of the film, so that certain selected areas of the film are substantially removed by the developer, while the desired remaining area on the substrate remains substantially intact. It may require considerable experimentation to optimize the formulation of the developer. For example, in a method where it is desired to preserve the area exposed to incident energy on the substrate, the use of a casting solvent to develop the film after exposure to incident radiation is too aggressive. Provide a dilute solution of the casting solvent in another liquid for an improved development method, in which (a) and the casting solvent are miscible; (b) the unexposed areas of the film are slightly soluble (It does not need to be completely dissolved); (c) The exposed area of the film is basically insoluble.

For example, in a preferred embodiment of the present invention, an amorphous film can be cast from a ketone solution. Using only ketone as a developer, or using a ketone-rich alcohol-ketone mixture, that is, a mixture containing more than 50 vol% ketone, will result in a development method that is less effective than a developer with alcohol as the main component. For example, a 10:1 (v/v) IPA:MIBK solution is a more effective developer for BaxSryTizO3(BST) than MIBK alone or 1:1 (v/v) IPA:MIBL, where IPA stands for isopropanol . The 10:1 mixture itself is not as effective as the 20:1 IPA:MIBK. However, both 10:1 and 20:1 solutions are more effective than 40:1 (v/v) IPA:MIBK. Furthermore, the relative effects of these solutions are closely related to other methods used in forming patterned films, including, for example, the type and energy of incident radiation and the substrate temperature during coating and patterning. Therefore, the determination of the appropriate developer formulation for the present invention requires experimentation, which is not obvious to those skilled in the art. For example, a liquid and/or solution-based developer can be physically applied in a manner similar to the development method used in the photoresist-based method described above.

After development, the at least partially converted precursor may optionally be processed by any of various methods known to those skilled in the art, and then subjected to a conversion method. These methods include but are not limited to annealing treatments such as thermal annealing, laser annealing or plasma annealing. Both the temperature and time of such annealing are important variables. The annealing step can also be affected by the previous surface treatment, such as oxygen plasma, laser, or rapid thermal annealing (RTA) methods. Appropriate conditions can be selected so that the at least partially converted precursor that has been annealed still maintains its amorphous properties, while at least one of its physical properties or electrical properties has been changed as required. In addition, depending on the application in which the film is to be used, annealing conditions that will cause the film to transform into a crystalline state, for example, high temperature may be desirable. For example, an appropriate heat treatment may be used at this stage to induce the formation of a highly oriented crystalline film from an at least partially transformed precursor that is amorphous or at least substantially amorphous. In this way, the properties of the amorphous film can be fine-tuned, or its physical properties can be varied in a wide range-from a completely amorphous phase at one extreme to a semi-crystalline mesophase to a single extreme at the other. Oriented crystal phase. Such heat treatment generally serves to further transform the precursor.

If the precursor is to undergo substantially sufficient conversion, then the precursor film is optional, but is typically subjected to the conversion process so that the precursor is substantially fully converted. The entire film or selected part of the precursor film can be exposed to the energy source. The conversion method may be an energy source, and the energy source may be the same as or different from any partial conversion method previously used. For example, the conversion method may be a light source with a special wavelength, a coherent light source with a special wavelength, a broadband light source, an electron beam source and/or an ion beam source. In certain embodiments of the invention, the energy source as discussed above, or at least part of the energy source, is a light source illuminated through an optical mask used to define an image on the surface. However, the energy does not have to be irradiated through the mask. For example, if it is not necessary to pattern the material in the conversion step, for example, because a pattern is already formed on the precursor, diffusion or coverage exposure can be used as the conversion method. Preferred conversion methods include light, electron beam, ion beam, and heat treatment. As discussed above for partial conversion, and also applied in this article, the atmospheric conditions under which the conversion is carried out, such as the composition of the atmosphere, pressure (including both total pressure and partial pressure), and humidity, are all Important process variables. During the conversion process, these variables can be the same as or different from the set values used in any previous partial conversion steps.

Of course, it should be understood that a preferred film, such as a mask, can be obtained by substantially fully converting at least a part of the partially converted precursor layer. The terms "substantially fully converted precursor" and "fully converted precursor" ", "transformed precursor", "substantially fully transformed partially transformed precursor", "fully transformed partially transformed precursor" and "transformed partially transformed precursor", as used herein, all Such a film is described.

It has been recognized that during the partial conversion and/or substantially full conversion of the precursor film into a film of the desired material, the film will undergo some shrinkage, which means that the thickness of the film of the desired material is often greater than that of the unconverted film. The precursor film is thinner. This change in thickness is an important feature of the present invention, which imparts useful properties to the film of the desired material. For example, for maximizing capacitance, forming an extremely thin film is advantageous, and at the same time, forming such a film is a challenge from a manufacturing point of view. The method of the present invention provides the ability to coat a thinner cast film, which gives convenience in manufacturing, but also provides a thinner film that needs to at least partially convert the precursor material, which also gives the required material The film gives improved performance. The shrinkage performance of the deposited film can be controlled and adjusted by wisely manipulating process variables. These variables include the selection of precursors, the selection of solvents and the amount of solvents, the types of precursor additives, the thickness of the precursor film determined by the deposition method, and the The heat treatment before, during and after the film is patterned, the development of the exposed film, etc. The method of the present invention allows precise control of the required film thickness range, so that the total thickness ranges from the angstrom () level to the micrometer (μm) level.

After the conversion, the subsequent optional operation steps may include post-conversion processing, including but not limited to the development step of the new development method as described above, and the post-development processing step. The specific steps should be selected according to the final application of the product. For example, the methods used are described in US 5,534,312, 5,821,017 and 6,071,676, and the contents of these patents are incorporated herein by reference.

In some embodiments of the present invention, after the conversion is an implantation step, at least one implantation region is formed on at least a portion of the substrate that is not substantially covered by the hard mask by using an implantation method. The use of ion beams as the implantation method is known in the art. However, this method is not limited to the use of ion beams, and any effective implantation method can be used. Ions suitable for implantation include, but are not limited to, arsenic, boron, and phosphorus. Ion implantation can be performed under the conditions of high energy combined with low dose, that is, energy higher than about 300KeV and dose of less than about 1020 atoms/cm2, or at low energy, that is less than about 300KeV, combined with high dose, that is, more than about 1020 atoms /cm2. The hard mask layer can optionally be removed after implantation. The implanted substrate may optionally undergo further processing, such as annealing, by which the implanted substrate region is converted into a doped region. If these two optional steps are carried out, the order in which they are carried out can be adjusted to suit the specific application involved in the present invention.

Other embodiments of the present invention envisage that at least part of the converted precursor formed by the method is used as an etch-resistant layer. In one or several etching steps, an etching method such as plasma, reactive ion or wet etching solution is used to provide a pattern through a hard mask to contact selected areas of the substrate, and only remove the substrate in these required areas. . Currently commonly used hard mask materials, such as silicon dioxide and silicon nitride, are used as protective masks in electronic manufacturing methods that use etching.

A preferred embodiment of the present invention envisages that the at least partially converted precursor or hard mask formed by the method is used as an etch-resistant layer. In one or several etching steps, etching methods such as plasma, reactive ions or wet etching solutions contact selected areas of the substrate through patterns provided by, for example, a hard mask, and remove the substrate only in these required areas. . Currently commonly used hard mask materials, such as silicon dioxide and silicon nitride, are used as protective masks in electronic manufacturing methods that use etching.

Figure 2 illustrates the basic sequence of the various steps for a preferred embodiment of the present invention, namely steps 2A, 2B, 2C and 2D, which are performed on the substrate 10 shown in step 2A before processing. For example, the substrate 10 may be a silicon wafer that has been coated with an organic layer. In step 2B, the unconverted precursor 11 is coated on the substrate 10. In step 2C, a conversion method, such as light in a photochemical metal organic deposition method, or heat treatment, is applied to at least a part of the unconverted precursor 11 to form the converted precursor layer 12. In step 2D, a removal method such as a developing composition is used to remove at least a part, preferably substantially all of the unconverted precursor layer 11, leaving a complete converted precursor layer 12, by which a hard mask of the substrate 10 is formed. Such a mask suitably allows certain patterning methods to pass through to the desired area of the substrate, while at the same time shielding or blocking certain other substrate areas from the patterning method.

In addition, in step 2C of FIG. 2, a partial conversion method, such as light or heat treatment, may be applied to at least a part of the selected unconverted precursor 11 to form the partially converted precursor layer 12. In step 2D, using a removal method such as a developing composition, at least part, preferably substantially all of the unconverted precursor layer 11 is removed, leaving a complete partially converted precursor layer 12. Then, at least a part of the precursor can be converted using a conversion method that is not shown in the figure, such as light or heat treatment, so that that part is substantially converted, thereby forming a hard mask. The partial transformation method and the transformation method can be the same or different. Figure 2 shows that steps are saved when forming a patterned hard mask by the method of the present invention.

In contrast, FIG. 3 illustrates the tedious prior art method of manufacturing a patterned hard mask. In step 3A, the substrate 200 is provided as illustrated in FIG. 2. In step 3B, a hard mask layer 210 is formed on the substrate. The hard mask layer may be silicon dioxide 210, for example. In step 3C, a photoresist layer 220 is coated on top of the hard mask layer 210. In step 3D, the photoresist layer 220 is exposed to light 230 through the mask 235. The mask 235 includes a transparent glass substrate 240, which has a region 250 that is substantially opaque to light, so that a part of the light is blocked, and a pattern is formed on the exposed portion 222 of the photoresist layer. In step 3E, the exposed photoresist area 222 is developed, and the hard mask layer 210 is exposed by the exposure. In step 3F, an opening 255 is formed in the hard mask layer 210 by etching away the unprotected portion of the hard mask layer 210 with a suitable etching composition. In step 3G, the remaining part of the photoresist 220 is removed. In step 3H, a plasma etching chemical that enables the substrate 200 to be etched without etching the hard mask layer 210 is selected to form a pattern on the substrate 200. This results in the pattern characteristics as defined in step 3I. Therefore, it can be clearly seen from FIG. 3 that, for manufacturing a patterned hard mask, the traditional method, such as ion implantation through a patterned mask, requires more steps than the method of the present invention.

Figure 4 illustrates a preferred embodiment of the method, used to manufacture a hard mask, using a metal complex precursor to form a patterned hard mask, this solution removes all steps related to hard mask etching , That is, the above steps 3C to 3G. In step 4A, the substrate 300 is supplied as illustrated in FIG. 2. In step 4B, a precursor layer 310, that is, a layer containing a metal complex, is formed on the top of the substrate 300. In step 4C, the precursor 310 is partially transformed by pancreatic lipase 320, where it is exposed to light 315. The mask 320 includes a transparent glass substrate 330 having regions 340 that are substantially opaque to partial conversion methods. Part of the precursor 310 exposed to the partial conversion method 315 is at least partially converted or reacted to form a region of the partially converted precursor 350. In step 4D, the entire assembly is exposed to a removal method (not shown), such as a liquid developer. The substantially unconverted precursor 310 is removed by a developer or removal method, exposing the substrate 310, while the partially converted precursor 350 that is partially converted and resistant to the removal method is retained. In step 4E, a conversion method (not shown) is applied to the partially converted precursor to form a substantially completely converted precursor 360, that is, a patterned hard mask. This conversion can be achieved by, for example, a diffuse light exposure step or a thermal annealing step. In each of steps 4C and 4E, if the converted precursor 360 is a dielectric film, the conversion is preferably performed in the presence of oxygen; and if the converted precursor 360 is a metal film, it is preferably performed in the presence of a reducing gas. In step 4F, the etching method forms a pattern on the substrate, and the etching method is selected to be plasma etching chemicals, which can etch the substrate 300 but cannot etch the mask layer 360. This forms the pattern feature 390 as defined in step 4G.

FIG. 5 illustrates a prior art method of forming TSI on a photoresist, for example, by generally known as a method of top silylation to form an image. In step 5A, a substrate 400 is provided. In step 5B, a photoresist layer 410 suitable for top silylation is coated on the substrate 400. In step 5C, the photoresist layer 410 is exposed to light 430 through the mask 435. The mask 435 includes a transparent glass substrate 440 having an area 450 that is substantially opaque to the exposure method, thereby blocking a part of the light, and forming a pattern on the exposed portion 432 of the photoresist layer. As a result of this exposure, different chemical and/or physical properties are given to the exposed photoresist regions. In step 5D, the substrate 400, the photoresist layer 410 and the exposed photoresist area 432 are all exposed to the gas TSI reagent 460, which is selectively absorbed into the exposed photoresist area 432 to form a modified Sexual photoresist surface 470. Examples of TSI reagent 460 are known in the art and include silicon-containing gases.

In step 5E, the surface is exposed to plasma treatment 480 to make the surface of the modified photoresist more inert, thereby forming a corrosion-resistant hard mask 490. In step 5F, plasma treatment 495 removes the photoresist 410 directly below the surface 490 of the corrosion-resistant hard mask. In step 5G, plasma treatment 497 is used to pattern the substrate 400, using photoresist The composite build-up layer formed by the layer 410, the modified photoresist surface 470 and the corrosion-resistant hard mask surface 490 determines the pattern transferred to the substrate 400. The resulting pattern is illustrated by the etching area 499 in step 5H. In In step 51, a removal method (not shown) is used to remove the composite build-up layer formed by the photoresist layer 410, the modified photoresist surface 470, and the corrosion-resistant hard mask surface 490. At the same time, the method illustrated in FIG. 5 It can provide advantages when forming a thin surface for pattern formation, which helps to improve the resolution that can be obtained, and multiple plasma treatment steps are required to relax the focal depth, which results in the disadvantage of requiring TSI reagents , And it involves increasing the cost and complexity of pattern transfer that does not exist in other traditional technologies.

In contrast, Figure 6 illustrates a preferred embodiment of the present method applied to TSI using a metal complex to form a patterned thin top surface. In step 6A, a substrate 500 coated with a pattern transfer layer 505 is provided. The pattern transfer layer 505 may optionally contain organic film-forming resins, which include photoresist, polyimide, PMMA, novolac resin, epoxy resin, and other organic or related coatings known to those skilled in the art. In step 6B, a precursor layer 510 is formed on the top of the substrate 500 to directly cover the pattern transfer layer 505. In this case, the precursor 510 contains a metal complex. In step 6C, the precursor is exposed to a partial conversion method through a mask 520, and light 515 is described here. The mask 520 includes a transparent substrate 530, such as a glass substrate, which has an area 540 that is substantially opaque to the partial conversion process. Part of the precursor 510 exposed to the partial conversion method 515 is at least partially converted or reacted to form a region 550 of the partially converted precursor. In step 6D, the entire assembly is exposed to a removal method (not shown) such as a liquid developer. The substantially unconverted precursor 510 is removed by a removal method such as a developer, exposing the pattern transfer layer 505, while leaving a partially converted precursor 550 that is partially converted and resistant to the removal method. In optional step 6E, a conversion method (not shown) is applied to the partially converted precursor 550 to form a substantially fully converted precursor 560. This conversion can be achieved by, for example, a diffuse light exposure step or a thermal annealing step.

In step 6F, the surface is exposed to an etching method 570, for example, a plasma etching chemical. For example, the plasma etching method may mainly consist of oxygen. The etching method removes the exposed area of the pattern transfer layer 505, and the partially converted or substantially fully converted precursor layer 560 is selected and processed so that it is basically inert to the etching method 570, thus forming an etching District 580. In step 6G, a pattern formed in the pattern transfer layer 505 under the at least partially converted precursor 560 is used to pattern the substrate 500 (not shown) by an etching method to form an etching area 590. In step 6H, the removal method (not shown) removes all the remaining pattern transfer layer 505 and at least part of the conversion precursor 560, exposing the desired patterned substrate 500 with the etched area 590. The method of Figure 6 is superior to the method shown in Figure 5 because it requires fewer steps, fewer plasma steps, and does not require TSI reagents. At the same time, the method of FIG. 6 retains all the advantages obtained by using the method of FIG. 5.

Figure 7 illustrates a prior art method of depositing a patterned metal layer on top of a substrate. This method is used when the required metal is difficult to etch, such as gold or platinum. In step 7A, a substrate 600 is provided. In step 7B, an isolation layer 605 is coated on the top of the substrate 600, and a lift-off layer 610 is coated on the top of the isolation layer 605. In step 7C, an optional hard mask layer 620 is deposited on top of the lift-off layer 710. In step 7D, a photoresist layer 630 is coated on top of the composite build-up layer composed of the optional hard mask layer 620, the lift-off layer 610, and the isolation layer 605. In step 7E, the photoresist layer 630 is exposed to light 645 through the mask 635. The mask 635 includes a transparent glass substrate 640 having a region 650 that is substantially opaque to the exposure method, so that a part of the light is blocked and a pattern is formed on the exposed portion 630 of the photoresist layer. In step 7F, a removal method, such as a wet developer, is used to remove the exposed portion 632 on the photoresist layer 630.

In step 7G, plasma etching chemicals 660 are used to etch through the optional hard mask layer 620 (if present). The plasma etching chemical 660 can also have the effect of eroding most of the thickness of the photoresist layer 630. In step 7H, a plasma etching chemical 670 is used to etch through the lift-off layer 610 and the isolation layer 605. In this step, the sidewalls can be manufactured. This can be achieved by first using plasma etching chemicals 670 in an anisotropic mode, for example, first moving the charged particles of the plasma in a vertical direction, and then converting to an isotropic mode This is achieved by making the charged particles responsible for etching in the plasma move evenly in all directions, and the sidewall is preferably curved as described in step 7H. In step 7I, a deposition method is used to cover the surface features with the desired metal 680 (eg, gold, platinum, or other desired metal). In step 7J, a removal method (not shown) such as solvent treatment is used to lift up all remaining isolation layer 605, lift-off layer 610, hard mask layer 620 (if present), and photoresist layer 630. This leaves only the required pattern of the required metal 680 on the substrate 600. This method of patterning metal deposits is very difficult, involves many steps, and requires the use of a thick photoresist layer. Such a thick photoresist layer consumes more than necessary and is very expensive. In addition, it is difficult to remove the photoresist because it is thicker than otherwise used.

In contrast, Figure 8 illustrates a preferred embodiment of the method, using a metal complex, applied to the lift-off method, to form a patterned thin top surface on the lift-off layer. In step 8A, a substrate 700 is provided. In step 8B, the isolation layer 705 is coated on the substrate 700, and the lift-off layer 710 is coated on the isolation layer 705. In step 8C, the precursor layer 720 is coated on the lift-up layer 710. In this case, the precursor 720 contains a metal complex. In step 8D, through the mask 735, the precursor 720 is exposed to a partial conversion method, where the partial conversion method is, for example, light 745. The mask 735 includes a transparent glass substrate 740 having areas 750 that are substantially opaque to the partial conversion process. A portion of the precursor 720 exposed to the partial conversion method 745 is at least partially converted or reacted to form a region of the partially converted precursor 732. In step 8E, the entire assembly is exposed to a removal method (not shown) such as a liquid developer. The substantially unconverted precursor 720 is removed by a developer or removal method, exposing the lift-up layer 710, while leaving a partially converted precursor 732 that is partially converted and resistant to the removal method. In an optional step (not shown), a conversion method (not shown) is applied to the partially converted precursor 732 to form a substantially fully converted precursor.

In step 8F, the removal method 760, such as plasma etching chemicals, is applied in an anisotropic manner to remove the regions of the lift-off layer 710 and the underlying isolation layer 705 that are not under the precursor 732. In step 8G, the lift-off layer 710 and the isolation layer 705 are etched in an anisotropic manner by the removal method 760, thereby forming a lift-off layer with a curved section as described. In step 8H, a film of the desired metal 770 is deposited on the assembly by a deposition method. In step 8I, by a development method, such as a solvent or dry development method, together with the precursor 732, the lift-off layer 710 and the isolation layer 705, the unnecessary part of the required metal 770 is removed, leaving all on the top of the substrate 700. The required pattern of metal 770 is required. This method is superior to the prior art method outlined in FIG. 7 because it requires fewer steps and does not require the use of photoresist.

Figure 9 illustrates another embodiment of the method, using a metal complex, applied to the lift-off method to form a patterned thin top surface film on the lift-off layer. In step 9A, a substrate 800 is provided. In step 9B, a precursor layer 810 is coated on the substrate 800. In this case, the precursor contains a metal complex. In step 9C, the precursor layer 810 is exposed to a partial conversion method through the mask 835, where the partial conversion method is, for example, light 845. The mask 835 includes a transparent glass substrate 840, which has an area 850 that is substantially opaque to the partial conversion process. Part of the precursor 850 exposed to this partial conversion method is at least partially converted or reacted to form an exposed area 832. In step 9D, the entire assembly is exposed to a removal method (not shown) such as a liquid developer. The substantially unconverted precursor 810 is removed by this removal method, exposing the substrate 800 while leaving exposed areas 832 that are partially converted and resistant to the removal method. As described in other embodiments of the present invention, the exposed area 832 may optionally be transformed after the method step 9D is removed. As described in step 9D, by controlling the exposure and the removal methods introduced in steps 9C and 9D, inwardly tapered sidewall sections can be obtained in the exposed area 832. These methods are as described in step 8D above. , 8F and 8G. In step 9E, a film of the desired metal 870 is deposited on the assembly by a deposition method. In step 9F, the unnecessary part of the required metal 870 is removed together with the precursor 832 by a developing method such as a solvent or dry developing method, leaving the required pattern of the metal 870 on top of the substrate 800.

In another preferred embodiment of the present invention, a TSI layer integration method can be used to manufacture a double corrugated structure used when copper is integrated into a semiconductor connector structure. Fig. 10 illustrates the prior art method of manufacturing the corrugated structure from step A to step H, and this method is called the "via-first" method. In step 10A, a substrate 900 is provided. As shown in the figure, the substrate is successively coated with a first dielectric layer 905, an isolation layer 915, a second dielectric layer 910, and a hard mask 920. The dielectric layers 905 and 910 are generally, but not necessarily, the same material, and the isolation layer and the mask layer 915 and 920 can be the same material or different materials, but are often silicon nitride and/or oxide silicon. In step 10B, on top of the hard mask 920, the assembly is coated with a bottom anti-reflective coating (BARC) 925 and a photoresist layer 930. As shown in the figure, a pattern is formed on the photoresist and developed by a conventional method. In step 10C, plasma etching chemicals are used to remove the portions indicated on the BARC layer 925, the hard mask 920, the dielectric layer 910, the isolation layer 915, and the dielectric layer 905. In step 10D, after the plasma method of step 10C, the remaining photoresist 930 and BARC layer 925 are removed from the assembly. In step 10E, as shown in the figure, a second BARC layer 935 and a second photoresist layer 940 are coated on the top of the assembly hard mask 920. The photoresist layer 940 is patterned and used by conventional methods. development. In step 10F, a second plasma etching chemical step is used to remove the BARC layer 935 and the specified portion of the dielectric layer 910. In step 10G, after the plasma method of step 10F, the remaining photoresist 940 and BATC 935 are removed.

In contrast, Figure 11 illustrates how the method of the present invention can produce a double corrugated structure in fewer steps. In step 11A, a substrate 1000 coated with a dielectric layer 1005 is provided. In step 11B, a precursor layer containing, for example, a metal complex is coated on top of the dielectric layer, and the pattern is formed by at least partial conversion, and then used as previously described in another embodiment of the present invention. The discussed technique is developed to obtain a patterned layer 1010 as shown in the figure. For example, the pattern development step can be performed by, for example, a solvent or a dry development method as described above. Then, a rotating planarization layer 1015 is coated on top of the patterned layer 1010. The rotating planarization layer 1015 can be any organic-based coating, and can be spin-coated on the assembly. In step 11C, as shown in the figure, the upper patterned layer 1020 is deposited, patterned, and developed, for example, using the same technique used when forming the patterned layer 1010. In step 11D, an etching method (not shown), such as plasma etching chemicals, is applied to remove the displayed area of the rotating planarization layer 1015 and a part of the thickness of the dielectric layer 1005. It is very important to control the etching method, as shown in the figure, to remove only a part of the thickness of the dielectric layer 1005. For example, plasma etching can be used to limit the time to be shorter than the time required to etch the entire thickness of the dielectric layer.

In step 11E, the patterned layer 1020 and the rotational planarization layer 1015 are removed by a removal method, such as treating the assembly with a solvent. The rotational planarization layer is soluble in the solvent, and the solvent affects other parts of the assembly. There are basically no adverse effects. In step 11F, a controlled etching method (not shown) is applied, such as plasma etching chemicals as described above, to remove the area depicted on the dielectric layer 1005. The controlled etching simultaneously removes the remaining thickness of the dielectric layer 1005 in the pattern formed by the patterned layer 1020, while only a part of the thickness of the dielectric layer 1005 is removed in the pattern formed by the patterned layer 1010. The double-corrugation pattern can be combined in this way.

After step 11F (not shown), the patterned layer 1010 can be optionally removed, and the patterned layer 1010 is left as a CMP termination point after copper deposition and planarization.

Obviously, the method described in Figure 11 is better than the method described in Figure 10, because the former uses fewer steps, does not require multilayer photoresist and BARC steps, and avoids the isolation layer used in the traditional method. And hard mask.

Fig. 12 illustrates a complicated ion implantation method simplified by the prior art for manufacturing a patterned ion implantation mask. In step 12A, a substrate 1200 is provided as described in FIG. 2. In step 12B, an optional protective layer 1205 is formed on the substrate 1200, and then a mask layer 1210 is implanted. In one embodiment, the implantation mask layer is silicon oxide. In step 12C, a photoresist layer 1220 is coated on the substrate 1200 on top of the implantation mask layer 1210. In step 12D, the photoresist layer 1220 is exposed to light 1230 through the mask 1235. The mask 1235 includes a transparent glass substrate 1240, which has an area that is substantially opaque to the exposure method 1250, and because it blocks a part of the light, a pattern is formed on the exposed portion 1222 of the photoresist layer. In step 12E, the exposed photoresist area 1222 is developed, exposing the injection mask layer 1210. In step 12F, an opening is formed in the implantation mask layer 1210 by etching away the unprotected part of the implantation mask layer with a suitable etching composition. In step 12G, the remaining part of the photoresist layer 1220 is removed. In step 12H, the substrate is exposed under an ion beam to directly form the implantation area 1270 under the opening in the implantation mask. In an optional step 12I, the implantation mask layer 1210 is removed, and the substrate is annealed, thereby converting the implantation region 1270 into a doping region 1280. Therefore, it can be clearly seen from FIG. 12 that the traditional method requires more steps than this method to form a patterned implant mask and perform ion implantation through the mask.

On the contrary, FIG. 13 illustrates another preferred embodiment of the method, which uses a metal complex to manufacture an ion implantation mask to form a patterned implantation mask. This method removes all steps related to the etching of the implantation mask. , That is, steps 12C to 12G as described above. In step 13A, a substrate 1300 is provided. In step 13B, an optional protective layer 1312 is formed on the substrate 1300, and a precursor layer 1310 is formed on top of the protective layer 1312. In this case, the precursor 1310 is a metal complex. In step 13C, the precursor 1310 is exposed to the partial conversion method through the mask 1320, where the partial conversion method is light 1315. The mask 1320 includes a transparent glass substrate 1330 with areas 1340 that are substantially opaque to the partial conversion process. A portion of the precursor 1310 exposed to the partial conversion method 1315 is at least partially converted or reacted to form a partially converted precursor region 1350. In step 13D, the assembly is exposed to a removal method (not shown), such as a liquid developer. The unconverted precursor 1310 is removed by a developer or a removal method, exposing the protective layer 1312, while leaving a partially converted precursor 1350 that is partially converted and resistant to the removal method. In step 13E, a conversion method (not shown) is applied to the partially converted precursor 1350 to form a substantially fully converted precursor 1360. This conversion can be achieved by, for example, a diffuse light exposure step or a thermal annealing step. In each of steps 13C and 13E, if the converted precursor 1360 will be a mesosite film, the conversion is preferably carried out in the presence of oxygen; and if the converted precursor will be a metal film, it is preferably in a reducing gas such as hydrogen. Existence. In step 13F, the substrate 1300 is subjected to an ion implantation method such as an ion beam 1370 to form an implanted region 1380 on the substrate. In optional step 13G, the implantation mask is removed and thermal annealing is performed to convert the implanted region 1370 on the substrate into a doped region 1390.

The wide range of the method of the present invention enables a wide range of applications. A preferred embodiment of the present invention includes an amorphous metal oxide film for forming an integrated capacitor structure in a printed wiring board (PWB), wherein a suitable precursor solution is used to coat and directly on the PWB substrate according to the present invention Form a pattern. The advantages of the present invention include the ability to directly form patterns, omit other process steps related to this, use the environmental temperature and pressure required for PWB processing, and the formed film is acceptable for high capacitance.

In another preferred embodiment, according to the present invention, a patterned metal oxide or mixed metal oxide film is formed on a transparent substrate to become an opaque pattern. In this way, the present invention can be used as a pattern mask when pattern transfer of lithography is performed in a semiconductor manufacturing method.

In another preferred embodiment of the present invention, an amorphous metal oxide or mixed metal oxide film is used to form a decoupling capacitor structure in the connection interface of an advanced connection semiconductor device. The flexible silicon substrate is coated with an appropriate precursor solution and patterned. The inherent advantages in this embodiment include the ability to directly form patterns, which can save many other process steps. Another advantage is the use of ambient temperature and ambient pressure, which are nothing compared to the conditions when such advanced connectors are assembled. different.

Another embodiment of the present invention envisages that the precursor film used can be used to pattern memory storage elements, whether in the form of a capacitive storage node, that is, dynamic random access memory (DRAM), or as a ferroelectric memory storage Node (FeRAM), in addition, the inherent advantages in this embodiment include the ability to directly form patterns, so that many other process steps are omitted, and another advantage is the use of ambient temperature and pressure, which are assembled with such memory devices Time is no different.

Another embodiment of the present invention envisages forming a gate dielectric material at the front end of a semiconductor product, because advanced silicon-based devices can convert silicon oxide into a new material with a higher dielectric constant among the preferred gate dielectric materials. This new material with high dielectric constant allows the physical thickness of the door dielectric material to be made thicker than silicon dioxide for the same electrical properties. The thicker physical thickness makes it easier to manufacture and also makes the quantum channel effect through the gate smaller. Obviously, when the method of the present invention is applied to a front-end-of-line (FEOL) semiconductor process, it has greater advantages than other known methods that require lower temperatures and strict low vacuum. There are a variety of high dielectric constant materials suitable for the method of the present invention, including but not limited to BaxSryTizO3 (BST), BaTiO3, SrTiO3, PbTiO3, PbxZryTizO3 (PZT), (Pb, La) (Zr, Ti) O3(PLZT), (Pb,La)TiO3(PLT), LiNbO3, Ta2O5, SrBi2Ti2O9, Al2O3, TiO2, ZrO2 and HfO2.

Similarly, the present invention can be used to manufacture gate electrode materials for FEOL semiconductor products. These materials are on top of the gate dielectric material that makes electrical contact with the gate dielectric material. In the past, the gate electrode has always been made of silicon. In a similar way to the migration of gate dielectric materials from silicon dioxide, there is a driving force to transform the gate electrode into a material with substantially better properties than silicon. Candidate materials for gate electrodes include platinum, iridium, ruthenium, ruthenium oxide, iridium oxide and other new materials. All these material proposals pose challenges for deposition and patterning, but they are all suitable for the application of the present invention. In addition, many steps in the traditional method require high temperatures, strict vacuum requirements, and harsh plasma processing conditions, all of which indicate that sensitive silicon substrates will be damaged. These harsh conditions can be avoided by using the method of the present invention. The greater challenge to the traditional method is that as described in US-P-6048769, different electrode materials need to be placed on gate transistors with different bias voltages. This requirement for the traditional integration path doubles the already many steps again. Therefore, from a manufacturing point of view, this preferred embodiment of the present invention provides a dramatic advantage for reducing the number of steps.

The application of precious metals and conductive metal oxides is not limited to the manufacture of gate electrodes. For these materials, there are several isolation layer applications, whether it is a conductive layer or an insulating layer, they are all used in the processing of FEOL semiconductors. Obviously, several of these applications rely on the formation of films of desired materials that have high dielectric constants (high k values) for use as capacitive materials. In a similar way, the film can be optimized to optimize the permeability (μ) of the film as an induction material. It may similarly be resistive elements, just like magnetic elements, piezoelectric elements, pyroelectric elements, and ferroelectric elements.

Other possible applications of the method of the invention are very broad. Some examples include: direct pattern deposition of high dielectric constant materials for semiconductor manufacturing (transistor gate groups, capacitive structures, etc.), direct patterning of high dielectric constant materials for microelectronic packages (capacitive structures) Deposition, low temperature deposition of high dielectric constant materials used in semiconductor manufacturing (transistor gate circuits, capacitive structures, etc.), low temperature deposition of high dielectric constant materials used in microelectronic packages (capacitive structures, etc.), used in semiconductors Non-vacuum-based deposition of high-dielectric constant materials for manufacturing (transistor gate circuits, capacitive structures, etc.), non-vacuum-based deposition of high-dielectric constant materials for microelectronic packages (capacitive structures, etc.), for semiconductors Direct pattern deposition of metal oxides for manufacturing (insulator structures, etc.), direct pattern deposition of metal oxides for microelectronic packages, low-temperature deposition of metal oxides for semiconductor manufacturing, and microelectronic packages (capacitive structures) Low-temperature deposition of metal oxides, non-vacuum-based deposition of metal oxides for semiconductor manufacturing, non-vacuum-based deposition of metal oxides for microelectronics packages, direct patterning of metals for semiconductor manufacturing (transistor gate circuits) Deposition, direct pattern deposition of metals for microelectronic packages (connectors, etc.), low-temperature metal deposition for semiconductor manufacturing, low-temperature metal deposition for microelectronics packages, non-vacuum-based metal deposition for semiconductor manufacturing, Metal non-vacuum-based deposition of microelectronic packages, direct pattern deposition of resistive materials for semiconductor manufacturing (on-chip resistive elements), direct pattern deposition of high-resistance materials for microelectronic packages (encapsulated resistors), for semiconductors Low-temperature deposition of resistive materials manufactured, low-temperature deposition of resistive materials for microelectronic packages (encapsulated resistors), non-vacuum-based deposition of resistive materials for semiconductor manufacturing, non-vacuum of resistive materials for microelectronic packages Base deposition, resistive materials controlled by mixed metal/oxide deposition, direct pattern deposition of sensor materials for semiconductor manufacturing (on-chip sensors), sensor materials for microelectronic packages (encapsulated sensors) Direct pattern deposition, low-temperature deposition of sensor manufacturing materials for semiconductor manufacturing, low-temperature deposition of sensor manufacturing materials for microelectronic packages (encapsulated inductors), and non-vacuum sensor manufacturing materials for semiconductor manufacturing -Based deposition, non-vacuum-based deposition of materials for the manufacture of inductors for microelectronic packages, direct pattern deposition of metal and oxide materials for the manufacture of devices using organic semiconductors and/or organic substrates, for the manufacture of organic semiconductors and / Or low-temperature deposition of metal and oxide materials for organic-based devices, for manufacturing

The supplementary description of the method for manufacturing electronic materials includes the content described in the concurrently filed US Patent Application 09/_____, titled "Method and Equipment for Substrate Pretreatment", the disclosure of which is incorporated herein by reference.

Examples The following examples further illustrate certain embodiments of the invention. These examples are provided for illustrative purposes only, and do not limit the present invention in any way.

Example 1 By dissolving it in a suitable solvent and spin-coating the solution on the surface of a silicon chip, two different zirconium-containing precursor films were cast, namely Zr (acetylacetone) 4 (also known as Zr (acac ) 4 and tetrakis (2,4-pentanedionyl) zirconium (IV)) and Zr (carboxylate) 4. Each of them is subjected to a long-term covering type heat treatment, that is, until the thickness of the precursor film no longer changes. After this treatment, a variable angle spectroscopic ellipsometer (VASE) was used to measure the relationship between the refractive index of each sample and the wavelength. The results obtained are depicted in Figure 14. In FIG. 14, the curve 101 is derived from a sample formed from a Zr(acac) 4 precursor, and the curve 102 is derived from a sample formed from a Zr (carboxylate) 4 precursor. These results show that there is a significant difference in the refractive index performance of each sample, which is directly related to the chemical composition of the precursor. The film formed from the Za(acac)4 precursor has a refractive index of 3%, which is higher than the refractive index of the film formed from Zr (carboxylate)4.

In Example 2, two different copper precursors were first produced, namely Cu(OH2)2(O2C(CH2)4CH3)4 and (μ-(C2H5)2NCH2CH2O)2Cu2(N3)2. It is believed that each precursor undergoes a photochemical reaction, which results in the loss of ligand and the production of copper atoms. Then it is thought that copper atoms combine with each other to form metallic copper, or combine with oxygen to form copper oxide. However, as a result of oxidation of the previously formed metallic copper, copper oxide may also be formed. Based on the chemistry of the prior art, there is no reason to assume that these different precursors will provide different products under similar conditions, although it is recognized that as a result of the selection of the precursor, the film-forming performance and efficiency of the reaction will be greatly improved. difference.

Therefore, each of these two precursors is dissolved, and each solution is deposited on a silicon wafer by spin coating, and then photodecomposed in a vacuum to make the precursor on each wafer coated The body layer undergoes substantially full conversion. The photolysis continues until the ligand-related absorption is no longer observed when the film is analyzed by DTIR spectroscopy. The sample was then transferred to a sintering furnace and heated under nitrogen at 400°C.

Then use the known wide-angle X-ray diffraction method to test each sample. It was found that the Cu(OH2)2(O2C(CH2)4CH3)4 precursor produced more copper oxide after conversion, while the (μ-(C2H5)2NCH2CH2O)2Cu2(N3)2 precursor produced more crystalline metal copper. Such results show the dependence of the results of these methods, that is, after the transformation, the composition of the precursor has a dependence that cannot be foreseen by the prior art.

The method of converting a film of a given precursor material into an amorphous film, such as a thermal method or a photolysis method, can have a significant impact on the performance of these films. As shown in Examples 3 and 4, this is shown in the aggregate optical refractive index data, which is also clearly shown by comparing the dielectric constant data.

Example 3 The precursor Zr(acac)4 (Zirconium(IV) acetylacetonate, from Chemat Technology, Northridge, CA) was dissolved in toluene, and the solution was spin-coated on a silicon wafer at a rotation speed of 1250 rpm and 30 sec. The thickness of the resulting unconverted precursor film was 436 angstroms. Heat the ZrO2 on a hot plate at 180°C for 1 hr to thermally convert the ZrO2. Prolonged thermal conversion is performed on a hot plate at 180°C. A Karl Suss MJB-3 mask aligner with 220nm cold mirror was used to perform photochemical conversion of ZrO2. Since the output intensity of the mask aligner in the deep ultraviolet region is relatively small (about 0.38mW/cm2), an exposure time of 5hr has to be used, because it has been found that no amount of exposure dose will further reduce the thickness. The relationship between the thickness and refractive index of the obtained film and the wavelength was measured using VASE. The measured thickness of these films is as follows: Unconverted Zr(acac)4 precursor 436thermal conversion 360extended thermal conversion 316light conversion 330 The precursor Zr(O(O)CC7H15)4 (Zirconium(IV) 2-ethylhexanoate, from Chemat Technology, Northridge, CA) was dissolved in hexane, and the solution was spin-coated at 1500rpm for 30sec On the silicon wafer. The thickness of the obtained unconverted precursor film was 2335 Å. The ZrO2 was heated on a hot plate at 180°C for 3 hours to thermally convert the ZrO2. Prolonged thermal conversion is performed on a hot plate at 180°C. Including the thermal conversion time, a total of 6hr is reached. As mentioned above for ZrO(acac)4, ZrO2 undergoes photochemical conversion, but because the precursor Zr(O(O)CC7H15)4 has relatively low light sensitivity and low exposure intensity, the exposure time used is about 30hr. It is also the relationship between the thickness of the film and the refractive index and the wavelength measured by VASE. The measured thickness of these films is as follows: Unconverted Zr(O(O)CC7H15)4 precursor 2335Body thermal conversion 1141Extended thermal conversion 977Light conversion 1487 shows the results of the refractive index in Figure 15. Here the photochemically converted Zr(acac)4 is curve 1, the thermally converted Zr(acac)4 is curve 2, and the thermally converted Zr(O(O)CC7H15) 4 is curve 3, and Zr(O(O)CC7H15)4 for photochemical conversion is curve 4, Zr(O(O)CC7H15)4 for extended thermal conversion is curve 5, and Zr(acac)4 for extended thermal conversion is curve 6.

These results show that there is a significant difference in the refractive index performance of each sample, which is directly related to the chemical composition of the precursor and its preparation method.

Example 4

A solution of about 7000 Å of the precursor in hexane was spin-coated on the aluminum-coated silicon wafer. The precursor was designed to obtain a BST film after at least partial conversion. By dissolving 3.7g Ti (bis(acetylacetone)bis(isopropoxy)), 2.8g barium 2-ethylhexanoate and 5.6g 2-ethylhexanoate (in 2-ethylhexanoic acid, concentration 40wt%) The BST precursor film was prepared in 182 g of hexane, which corresponds to a molar ratio of Ba:Sr:Ti(IV) of 1:0.8:1. The precursor film is converted into a BST film by heat treatment or by photodecomposing the material. The obtained thin BST film was made into a film capacitor and the electrical properties of the film were measured. As can be seen from the results below, the dielectric constant and average conductivity of each film are dramatically different: BST film obtained by thermal conversion has a dielectric constant of 4.66 average conductivity 0.009992S BST film obtained by photochemical conversion The dielectric constant is 27.26 and the average conductivity is 0.04311S. These results show that for each sample, there is a significant difference in electrical properties, which is directly related to the preparation method of the conversion precursor.

In Example 5, for example, when the film precursor is spin-coated, the choice of solvent is important because it can affect the optical quality of the film. For example, this example shows that a film obtained by casting a solution containing a precursor for conversion into a BST film in MIBK and n-heptane can obtain a very high optical quality, while a streaked film can be obtained from a solution of PGMEA membrane.

In each of these solvents, the precursor is dissolved in the solvent, or a part or all of the solvent in the precursor solution is replaced with a desired solvent. Each solution was deposited on a silicon wafer covered with aluminum by spin coating. The silicon wafer is rotated at 1500 rpm for 30 sec. After spin coating, bake on the 110 hot plate for 2 minutes to remove any remaining solvent. A Karl Suss MJB-3 mask aligner with a 220nm cold mirror was used to convert the precursor film into oxide with an intensity of about 1.2mW/cm2. Each wafer is exposed for 1.5hr to ensure complete conversion. After the conversion, the development and removal steps are carried out. At this time, rinse with the same solvent as the spin-coated sample to wash off the unconverted and unexposed parts of each precursor film. VASE was used to measure the film thickness before conversion (ie, unconverted), immediately after conversion, and after development.

The surface of the precursor film with high optical quality obtained from MIBK and n-heptane has basically no surface features, so there is no picture to show this. On the contrary, the BST precursor film spin-coated from the PGMEA solution showed obvious streaks, which can be seen in FIG. 16. Among the above solvents, MIBK produces the most uniform and reproducible film.

Example 6 In the example of how to use heat treatment to convert the precursor film into the film of the desired material, a series of bare silicon wafers were spin-coated with the precursor solution designed to form the BST film during the conversion. By heating each wafer on a heating plate at 160° C. at intervals of 10 min, the total heating time is 120 min, so that the wafer is at least partially converted. After each conversion interval, the precursor pattern was developed by rinsing with isopropanol to remove the unconverted precursor. In this way, it is possible to determine the time required to heat-print the film, that is, the time required to have a significant amount of residual film after development with isopropanol. As can be seen in Figure 17, for the thermal conversion, the measured time is approximately 20 minutes.

A similar experiment was performed with photochemical conversion instead of thermal conversion, and the results are shown in FIG. 18. The figure shows that the time required for photochemical printing of the film is about 30 to 60 minutes. In the third experiment, the design was to combine thermal partial conversion or pretreatment with photochemical conversion. The wafer was preheated at 160°C for 10 minutes, and then the photochemical conversion was performed as described above. The result of thermal/photochemical printing is shown in Figure 19, which shows that the time required for the combined thermal/photochemical conversion method, that is, the maximum time required to form a pattern, has been shortened from 30-60 minutes for photochemical conversion alone to approximately 20min.

Embodiment 7 Both shortening the wavelength of the imaging light and increasing the digital aperture of the lens system can improve the resolution of the light projection system. However, the ability to maintain image focus on the entire photoresist film decreases as the thickness increases. Reducing the thickness of the photoresist film can maintain the depth of focus, but the requirement for the etching required for the pattern transfer step limits the maximum thickness of the photoresist. In order to weaken the limitation of the depth of focus, a thin film is used for imaging, only forming a pattern on the top layer of photoresist. After imaging the top layer of photoresist, the pattern is developed and then transferred to the substrate using an etching method.

For the two-layer method using a metal complex precursor, two sets of films containing a bottom layer and a metal complex precursor can be used, each layer being, for example, spin-coated. The role of the metal complex precursor is the requirement of the etching mask, and the bottom layer is used to transfer the pattern to the substrate using etching. Three different substrates were tested: PMMA, PHOST and novolac resin. PHOST and novolac resins were hard baked on a hot plate at 160°C for 2 hours and then spin-coated the metal complex precursors. The metal complex precursor used in the experiment was designed to form BST, PZT or titanium dioxide (TiO2). The BST precursor was prepared according to the procedure described in Example 4. By dissolving 18.48g of lead 2-ethylhexanoate in 57.4g of hexane, adding 24.2g of zirconium(IV) 2-ethylhexanoate and 9.5g of Ti (bis(acetylacetone)bis(isopropoxy)), Then, 327 g of hexane was added to prepare the PZT precursor, which corresponds to a molar ratio of Pb(II):Zr(IV):Ti(IV) of 2.5:1:1.3. The following table lists the different combinations used and whether the underlayer and metal complex precursor are considered compatible.

The relative compatibility of the bottom layer precursor using hexane casting solvent PMMA BST Poor PMMA PZT Poor PHOST BST Poor PHOST PZT Poor novolac resin BST Good novolac resin PZT Good novolac resin TiO2 Good discovery of hard-baked novolac resin and BST , PZT and TiO2 precursors are all compatible, while the tested PMMA and PHOST base materials will dissolve when the metal complex layer is spin-coated. PMMA and PHOST will dissolve in the presence of the casting solvent hexane used for BST and PZT precursors. The compatibility of the hard-baked novolac resin with BST and PZT enables pattern formation and transfer.

In Example 8, the etching selectivity between the hard-baked novolak resin and the two metal complexes was determined by monitoring the thickness change during etching. Prepare hard-baked novolac resin and fully converted samples of PZT or TiO2 according to Example 7. Load the samples into the etching chamber and etch them with oxygen plasma at 30sec intervals. The total etching time is at least 120sec. The thickness of the sample is measured after each etching interval. Determine the etching rate of each sample from the thickness vs. etching time graph. Figure 20 shows a graph of the thickness of the hard-baked novolac resin versus etching time, while Figure 21 is the same graph for fully converted PZT and TiO2. The following table lists the respective slopes and correlation coefficients of linear least squares lines. Oxygen etched layer Thickness ~ slope of the etching time graph Correlation coefficient Hard bake novolac -76.3 0.999 fully converted PZT -0.195 0.985 fully converted TiO2-0.0866 0.992 The etching selectivity is determined by the slope ratio of each etching speed map. The etching selectivity between hard-baked novolac resin and fully converted PZT is about 390:1. The etching selectivity between hard-baked novolac resin and fully converted TiO2 is about 880:1. Under the same conditions, the etching selectivity of TIO2 is roughly equivalent to that of SiO2.

Example 9 carried out the electron beam contrast test of BST and PZT. By exposing a series of fully converted films of each material, the dose of electron beam was increased, and it was noted that the percentage of the film retained after development was 0. The highest dose and retention The ratio of the film reaches the minimum dose of 1 to determine the speed of light of these materials. The contrast ratio of PZT and BST is about the same range, from about 60 to about 100 μC/cm2.

Those skilled in the art will be able to understand that the scope of the present invention is not limited to the content disclosed herein, but also includes its expanded content.