Method for producing an electronic device having a multi-layer structure.

Description: TECHNICAL FIELD [Detailed description of the invention]

[Industrial application field] The present invention relates to, for example, a method for forming a thin film multilayer structure such as a thin film semiconductor element, a photovoltaic element, and a photosensitive device for electrophotographic. [Conventional technology] Conventionally, for functional films, particularly amorphous to polycrystalline semiconductor films, a film forming method suitable for each has been adopted from the viewpoint of desired physical properties, applications, and the like. For example, amorphous or polycrystalline non-single crystal silicon whose unpaired electrons are compensated with a compensator such as hydrogen atom (H) or halogen atom (X), if necessary (hereinafter referred to as "NON-Si (H)". , X) , and among them, A-Si (H, X) when indicating amorphous silicon, and poly-Si (H, X) when indicating polycrystalline silicon. The vacuum deposition method is used to form silicon-based deposited films such as films (it goes without saying that microcrystalline silicon is in the category of A-Si (H, X)). Plasma CVD method, thermal CVD method, reaction sputtering method, ion plating method, optical CVD method and the like have been tried, and in general, the plasma CVD method is widely used and commercialized. [Problems to be solved by the invention] Therefore, the reaction process in the formation of a silicon-based deposition film by the plasma CVD method, which has been generally used in the past, is considerably more complicated than that of the conventional CVD method, and the reaction mechanism is unclear. Not a few. In addition, there are many parameters for forming the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure at the time of formation, high frequency power, electrode structure, structure of reaction vessel, exhaust speed, plasma generation method, etc.). Due to the combination of many parameters, the plasma sometimes became unstable, which often had a significant adverse effect on the formed sedimentary film. Moreover, the parameters specific to the device must be selected for each device, and therefore it is difficult to generalize the manufacturing conditions. On the other hand, in order to develop a silicon-based deposition film that can sufficiently satisfy the electrical and optical characteristics for each application, it is currently best to form it by the plasma CVD method. Therefore, depending on the application of the silicon-based sedimentary film, it is necessary to fully satisfy the large area, film thickness uniformity, and film quality uniformity for mass production with reproducibility. Therefore, silicon by the plasma CVD method is used. In the formation of the system deposition film, a large amount of capital investment is required for mass production equipment, the management items for mass production are complicated, the management tolerance is narrow, and the adjustment of the equipment is delicate. It has been pointed out that this is a problem that should be improved in the future. Further, in the case of the plasma CVD method, since plasma is directly generated by high frequency or microwave in the film forming space where the film-forming substrate is arranged, the generated electrons and a large number of ion species Causes damage to the film during the film formation process, resulting in deterioration of film quality and non-uniformity of film quality. In particular, in the case of a semiconductor device having a multi-layer structure, it is known that the interface state between each layer greatly affects the characteristics of the device. Therefore, for example, in the case of producing an electrophotographic photosensitive member, when the light reflection prevention layer, the charge injection prevention layer, the photosensitive layer, the surface protection layer and the light absorption increase layer are deposited on the substrate, the raw material gas type, the flow rate, and the like are used. Since the plasma discharge intensity and the like differ greatly for each layer, the discharge is stopped and complete gas exchange is performed, the gas type, flow rate, and plasma discharge intensity are gradually changed to provide a changing layer, or each deposited layer is provided. By forming in separate deposition chambers, the interface state between each deposition layer is improved and the element characteristics are improved. However, no satisfactory improvement in device characteristics was observed by any of these methods. As mentioned above, there are still many points to be solved in the formation of the silicon-based sedimentary film, and mass production is carried out with low-cost equipment while maintaining its practical characteristics and uniformity. The development of a forming method that can be transformed is eagerly desired. In particular, the development of a forming method for improving the interface state of a thin film multilayer structure such as a thin film transistor, a photovoltaic device, and an electrophotographic photosensitive member and a thin film multilayer structure having a good interface state and improving the characteristics of the device or the like is desired. There is. [Means to solve problems] The method for forming a thin film multilayer structure according to the present invention is a method for forming a thin film multilayer structure having a forbidden bandwidth controlled semiconductor thin film, in which at least one layer of the semiconductor thin film is formed by an optical CVD method and at least one layer of the other thin films is formed. A plurality of gaseous raw materials for forming a depositary film and a gaseous halogen-based oxidizing material having a property of oxidizing the raw materials, which are introduced into the reaction space and brought into contact with each other to contain a precursor in an excited state. The precursors of the above are chemically produced, and at least one of these precursors is formed as a source of the sedimentary film constituents. [Explanation of action, etc.] According to the method for forming a thin film multilayer structure according to the present invention, a multilayer structure having good interfacial characteristics can be obtained, and the formation of each deposited layer is sufficient for energy saving, film thickness uniformity, and film quality uniformity. This simplifies management and mass production, does not require a large capital investment for mass production equipment, clarifies the management items for mass production, has a wide management tolerance, and makes it easy to adjust the equipment. .. The gaseous raw material is oxidized by contact with a gaseous halogen-based oxidizing agent, and is appropriately selected as desired depending on the type, characteristics, application and the like of the target deposited film. In the present invention, the above-mentioned gaseous raw material and gaseous halogen-based oxidizing agent may be any gas as long as they are introduced into the deposition chamber and made into a gaseous substance when they come into contact with each other. However, it does not matter whether it is a liquid or a solid. When the raw material or halogen-based oxidant for forming the deposition film is a liquid or solid, Ar, He, N₂, H₂Using a carrier gas such as the above, bubbling is performed while applying heat as necessary to introduce a raw material for forming a sedimentary film and a halogen-based oxidizing agent into the reaction space as a gas. At this time, the partial pressure and mixing ratio of the gaseous raw material and the gaseous halogen-based oxidant are adjusted by adjusting the flow rate of the carrier gas or the vapor pressure of the raw material for forming the deposit film and the gaseous halogen-based oxidant. Set. As the principle material for forming a deposit film used in the present invention, for example, if a tetrahedral deposit film such as a semiconductor or electrically insulating silicon deposit film or a germanium deposit film is to be obtained, a straight chain is used. Typical and branched chain silane compounds, cyclic silane compounds, chain germanium compounds and the like can be mentioned as effective ones. Specifically, as a linear silane compound Si_nH_{2n + 2}(n = 1,2,3,4,5,6,7,8), as a branched chain silane compound, SiH₃SiH (SiH)₃) SiH₂SiH₃, Si as a cyclic silane compound_nH_2n(n = 3,4,5,6) and the like. Of course, these raw material substances can be used not only by one kind but also by mixing two or more kinds, and can be used as a raw material gas when forming a sedimentary film by the optical CVD method. The halogen-based oxidant used in the present invention is made gaseous when introduced into the reaction space, and at the same time, it is effective only by contacting with the gaseous raw material for forming a deposit film introduced into the reaction space. It has the property of oxidatively acting, and is F.₂, Cl₂, Br₂, I₂Halogen gas such as, fluorine in the developing state, chlorine, bromine and the like can be mentioned as effective ones. These halogen-based oxidants are in the form of a gas, and are introduced into the reaction space together with the gas of the raw material for forming the deposit film at a desired flow rate and supply pressure, and are mixed and collided with the raw material. By chemically contacting the raw material, the raw material is oxidized to efficiently produce a plurality of kinds of precursors including the precursor in the excited state. The excited state precursors and multiple precursors produced serve as a source of components of the sedimentary membrane on which at least one of them is formed. The resulting precursor decomposes or reacts to become a precursor in another excited state or a precursor in another excited state, or releases energy as needed but forms a film as it is. By touching the surface of the substrate arranged in the space, a three-dimensional network structure deposit film is formed when the substrate surface temperature is relatively low, and a crystalline deposit film is formed when the substrate surface temperature is high. In the present invention, the deposition film formation process proceeds smoothly, and a film having high quality and desired physical characteristics can be formed. The combination, the mixing ratio of these, the pressure at the time of mixing, the flow rate, the pressure in the film forming space, the gas flow type, and the film forming temperature (base temperature and atmospheric temperature) are appropriately selected as desired. These film forming factors are organically related and are not determined independently, but are determined individually in relation to each other. In the present invention, the ratio of the amount of the gaseous raw material for forming the deposit film introduced into the reaction space to the gaseous halogen-based oxidizing agent is related to the relationship between the film forming factors and the related film forming factors. Although it is appropriately determined as desired, the introduction flow rate ratio is preferably 1/20 to 100/1, more preferably 1/5 to 50/1. The pressure at the time of mixing when introduced into the reaction space should be higher in order to stochastically increase the contact between the gaseous raw material and the gaseous halogen-based oxidizing agent, but the reactivity is taken into consideration. Then, it is preferable to determine the optimum value as desired. The pressure at the time of mixing is determined as described above, but the pressure at the time of introduction is preferably 1 × 10.^-7Atm ~ 5 atm, more preferably 1 x 10^-6It is desirable that the pressure is ~ 2 atm. The pressure in the film-forming space, that is, the pressure in the space in which the substrate to be film-formed is arranged on the surface thereof, is the precursor (E) in the excited state generated in the reaction space and, in some cases, the precursor. The precursor (D) derived from the body (E) is appropriately set as desired so as to effectively contribute to the film formation. When the film formation space is openly continuous with the reaction space, the internal pressure of the film formation space is the introduction pressure in the reaction space between the substrate-like raw material for forming the deposition film and the gaseous halogen-based oxidant. And in relation to the flow rate, it can be adjusted by adding ingenuity such as differential exhaust or use of a large exhaust device. Alternatively, when the conductance of the connection portion between the reaction space and the film forming space is small, it is possible to adjust the pressure in the film forming space by providing an appropriate exhaust device in the film forming space and controlling the exhaust amount of the device. You can. Further, when the reaction space and the film forming space are integrated and the reaction position and the film forming position are only spatially different, differential exhaust is performed as described above, or a large size having sufficient exhaust capacity is provided. Exhaust device should be provided. As described above, the pressure in the film forming space is determined by the relationship between the introduction pressure of the gaseous raw material and the gaseous halogen oxidant introduced into the reaction space, but is preferably 0.001 Torr to 100 Torr. It is preferably 0.01 Torr to 30 Torr, and optimally 0.05 to 10 Torr. Regarding the gas flow type, when the raw material for forming the deposit film and the halogen-based oxidant are introduced into the reaction space, these are uniformly and efficiently mixed, and the precursor (E) is efficient. It is necessary to consider the geometrical arrangement of the gas introduction port, the substrate, and the gas exhaust port so that the gas introduction port, the substrate, and the gas exhaust port can be properly formed. One of the preferred examples of this geometric arrangement is shown in FIG. 1, as described below. The substrate temperature (Ts) at the time of film formation is individually set as desired according to the type of gas used, the type of deposited film to be formed, and the required characteristics, but an amorphous film is used. When obtained, it is preferably from room temperature to 450 ° C, more preferably 50 to 400 ° C. In particular, when forming a silicon deposition film having better semiconducting and photoconductive properties, it is desirable that the substrate temperature (Ts) is 70 to 350 ° C. Further, when a polycrystalline film is obtained, it is preferably set to 200 to 700 ° C, more preferably 300 to 600 ° C. As for the atmospheric temperature (Tat) of the film formation space, the precursor (E) and the precursor (D) to be produced do not change into chemical species unsuitable for film formation, and the precursor (E) is efficiently produced. ) Is generated as desired in relation to the substrate temperature (Ts). FIG. 5 is a schematic configuration diagram of an apparatus for forming a sedimentary film whose bandgap is controlled by the optical CVD method. In the figure, 501 is a film forming chamber as a film forming space, has a substrate support 502 inside, and a desired substrate 503 is placed on the substrate support 502. Reference numeral 504 is a heater for heating the substrate, and power is supplied through the lead wire 505 to generate heat. Reference numerals 506 to 509 are gas supply sources, and are provided according to the type of the compound gas containing a silicon-containing compound, a hydrogen, a halogen compound, an inert gas, and an impurity element serving as a forbidden band width adjusting agent. When a liquid of these raw material compounds is used in the standard state, an appropriate vaporizer is provided. In the figure, the signs of the gas supply sources 506 to 509 are marked with a for the branch pipe, marked with b for the flow meter, and marked with c for the pressure gauge that measures the pressure on the high pressure side of each flow meter, d. Or, attached with e is a valve for adjusting each gas flow rate. The gas of the raw material compound is introduced into the film forming chamber 501 via the introduction tube 510. Reference numeral 512 denotes a photoenergy generator, in which the light energy acts on the raw material gas flowing in the direction of arrow 514 to excite and decompose the acted compound, and the decomposed compound chemically reacts. A deposit film having a controlled forbidden band width is formed on the substrate 503. Reference numeral 515 is an exhaust valve, and reference numeral 516 is an exhaust pipe, which are connected to an exhaust device (not shown) for vacuum exhausting in the film formation space. Further, as the high-energy light used in the method of the present invention, for example, light generated by a low-pressure mercury lamp, a xenon lamp, a carbon dioxide gas laser, an argon ion laser, an excimer laser or the like can be used. The light energy used in the present invention is not limited to ultraviolet energy, and the wavelength range does not matter as long as it can excite, decompose or polymerize the raw material gas and deposit the decomposition product. It also excludes the case where light energy is absorbed by the raw material gas or the substrate and converted into heat energy, and the heat energy causes excitation / decomposition or polymerization of the raw material gas to form a deposit film. Absent. When using such a device, for example, to form a sedimentary film with a controlled bandgap, a suitable substrate 503 is placed on the support 502 and an exhaust pipe (not shown) is used to install the exhaust pipe. The inside of the film forming tube 501 is exhausted through the film to reduce the pressure. Then, if necessary, the substrate is heated, and SiH is released from the gas supply cylinder.₄, H₂Raw material gas and forbidden bandgap adjuster O₂.GeH₄, CH₄The raw material gas such as, etc. is introduced into the film forming chamber 501 through the gas introduction pipe 510, and while maintaining the pressure in the film forming chamber at a predetermined pressure, the light energy generator irradiates the film forming chamber 501 with light 513. A deposit film with a controlled forbidden band width is formed on the substrate 503. Among the forbidden bandgap adjusting agents used in the present invention, examples of the compound containing the forbidden bandgap expanding element include a carbon-containing compound, an oxygen-containing compound, and a nitrogen-containing compound. Specifically, as a carbon-containing compound, CH₄, C₂H₆, C₃H₈, C₄H₁₀General formula C such as_nH_{2n + 1}Compound represented by (n is a natural number), C₂H₄, C₃H₆, C₄H₈... etc. General formula C_nH_2nCompound represented by (n is a natural number), C₂H₂, C₆H₆And other compounds can be mentioned. As an oxygen-containing compound, O₂, CO₂, NO, NO₂, N₂O, O₃, CO, H₂O, CH₃OH, CH₃CH₂Compounds such as OH can be mentioned. As a nitrogen-containing compound, N₂, NH₃, N₂H₅N₃, N₂H₄, NH₄N₃And so on. Further, as the compound containing the forbidden bandgap reducing element, for example, a chain germanium compound, a tin compound and the like can be mentioned as effective ones. Specifically, as a chain germanium compound, Ge_mH_{2m + 2}(m = 1,2,3,4,5) etc., and as a tin compound, for example, SnH₄Such as tin hydride can be mentioned. Although the method of forming a sedimentary film having a controlled forbidden bandgap and the method of forming a sedimentary film having a controlled forbidden bandgap are different, both of the means for forming a sedimentary film are the same. It may be arranged inside. However, when using either one of the forming means, it is necessary to stop the other forming means. It is also possible to connect both of the above-mentioned deposit film forming means via a gate valve or the like to continuously form both of the deposit film. Further, as the valence electron controlling agent for forming the valence electron controlled deposition film, in the case of a silicon-based semiconductor film and a germanium-based semiconductor film, a period in which it acts as a p-type valence electron controlling agent, a so-called p-type impurity. Elements of Group III A in the rate table, for example compounds containing B, Al, Ga, In, Tl, etc., and n-type valence control agents, elements of Group V A in the periodic table that act as so-called n-type impurities, for example. Compounds containing N, P, As, Sb, Bi and the like can be mentioned. Specifically, NH₃, HN₃, N₂H₅N₃, N₂H₄, NH₄N₃, PH₃, P₂H₄, AsH₃, SbH₃, BiH₃, B₂H₆, B₄H₁₀, B₅H₉, B₅H₁₁, B₆H₁₀, B₆H₁₂, Al (CH₃)₃, Al (C₂H₅)₃, Ga (CH₃)₃, In (CH₃)₃Etc. can be mentioned as effective ones. In addition, these valence electron control agents can also be used as a forbidden bandgap adjusting agent by adding a large amount. The substrate used in the present invention may be conductive or electrically insulating as long as it is appropriately selected as desired according to the use of the deposited film to be formed. Examples of the conductive substrate include metals such as NiCr, stainless steel, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt and Pd, or alloys thereof. As the electrically insulating substrate, a synthetic resin film or sheet such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, or polyamide, glass, ceramic, or the like is usually used. It is desirable that at least one surface of these electrically insulating substrates is conductively treated, and another layer is provided on the surface side of the conductively treated surface. For example, in the case of glass, its surface is NiCr, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In.₂O₃, SnO₂, ITO (In₂O₃+ SnO₂), Etc., or if it is a synthetic resin film such as a polyester film, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, The surface is conductively treated by vacuum-depositing, electron-beam-depositing, sputtering or the like with a metal such as Ti or Pt, or laminating with the metal. The shape of the support can be any shape such as a cylinder, a belt, a plate, and the like, and the shape is determined as desired. The substrate is preferably selected from the above in consideration of the adhesion and reactivity between the substrate and the film. Furthermore, if the difference in thermal expansion between the two is large, a large amount of strain will occur in the film, and a film in a good product room may not be obtained. Therefore, select and use a substrate in which the difference in thermal expansion between the two is close. Is preferable. Further, since the surface state of the substrate is directly related to the structure (orientation) of the film and the generation of the chain structure, the surface of the substrate is treated so as to obtain the film structure and the film structure so as to obtain the desired characteristics. Is desirable. [Example] Hereinafter, examples of the present invention will be described in detail with reference to the drawings. First, FIG. 1 is a schematic configuration diagram of a sedimentary film forming apparatus for carrying out the method for forming a thin film multilayer structure according to the present invention. The equipment shown in the figure is roughly divided into three types: the equipment body, the exhaust system, and the gas supply system. The main body of the device is provided with a pipe for introducing gas and a light energy generator. 101 to 108 are cylinders filled with gas used for film formation, 101a to 108a are gas supply pipes, 101b to 108b are mass flow controllers for adjusting the gas flow rate from each cylinder, 101c. ~ 108c are gas pressure gauges, 101d ~ 108d and 101e ~ 108e are valves, respectively, and 101f ~ 108f are pressure gauges that indicate the pressure in the corresponding gas cylinders, respectively. Reference numeral 120 denotes a vacuum chamber, which is provided with a pipe for gas introduction at the upper part, has a structure in which a reaction space is formed downstream of the pipe, and a base 118 is installed facing the gas discharge port of the pipe. It has a structure in which a film-forming space provided with the substrate holder 112 is formed. The gas introduction pipe has a triple concentric arrangement structure, the first gas introduction pipe 109 in which the gas from the gas cylinders 101 and 102 is introduced, and the second gas in which the gas from the gas cylinders 103 to 105 is introduced. It has an introduction pipe 110 and a third gas introduction pipe 111 into which gas from gas cylinders 106 to 108 is introduced. For gas discharge into the reaction space of each gas introduction pipe, it is designed to be arranged at a position farther from the surface position of the substrate so that the position becomes the inner pipe. That is, each gas introduction pipe is arranged so as to surround the inner pipe as it becomes the outer pipe. The gas supply from the pipe cylinder to each introduction pipe is made by the gas supply pipelines 123 to 125, respectively. Each gas introduction pipe, each gas supply pipeline, and the vacuum chamber 120 are evacuated by a vacuum exhaust device (not shown) via the main vacuum valve 119. The base 118 is appropriately installed at a desired distance from the position of each gas introduction pipe by moving the base holder 112 up and down. In the case of the present invention, the distance between the substrate and the gas discharge port of the gas introduction pipe is in an appropriate state in consideration of the type of the deposited film to be formed, its desired characteristics, the gas flow rate, the internal pressure of the vacuum chamber, and the like. It is preferably determined to be several mm to 20 cm, more preferably about 5 mm to 15 cm. 113 is a substrate heater that heats the substrate 118 to an appropriate temperature during film formation, preheats the substrate 118 before film formation, and further heats the substrate 118 to anneal the film after film formation. is there. The substrate heater 113 is supplied with electric power by the power supply 115 by the lead wire 114. The 116 is a thermocouple for measuring the temperature of the substrate temperature (Ts) and is electrically connected to the temperature display device 117. 126a and 126b are light energy generators for supplying light energy into the vacuum chamber 120. 127a and 127b are windows for irradiating light energy into the vacuum chamber 120. Using such a deposition film forming apparatus, a method for manufacturing a solar cell having a thin film multilayer structure, a photosensitive device for electrophotographic, and a thin film transistor (hereinafter referred to as TFT) according to the present invention will be specifically described. (Example 1) FIG. 2 is a schematic configuration diagram of a solar cell which is the first embodiment of the thin film multilayer structure according to the present invention. In the figure, a transparent electrode (not shown), a p-type amorphous silicon carbide layer 201 (first layer, thickness 300 Å), and an i-type amorphous silicon layer 202 (second layer) are placed on the glass substrate 200. A layer (thickness 1 μm), an n-type amorphous silicon layer 203 (third layer, thickness 200 Å), and an Al electrode 204 are laminated. When the p-type amorphous silicon carbide layer 201 is deposited, the SiH of the cylinder 101 is used.₄B of cylinder 103 from gas introduction pipe 109 at a flow rate of 20 SCCM₂H₆/ He gas (B)₂H₆Concentration 1000ppm) with flow rate 3SCCM and cylinder 105 CH₄Gas was introduced into the vacuum chamber 120 from the gas introduction pipe 110 at a flow rate of 100 SCCM and He gas from the cylinder 107 from the gas introduction pipe at a flow rate of 20 SCCM, respectively, and 15 mw / cm from the low-pressure mercury lamps 126a and 126b.²Irradiate the light of. As a result, a p-type amorphous silicon carbide layer 201 whose forbidden band width was expanded by carbon was formed. Therefore, the window effect is improved and the photoelectric conversion efficiency is improved. In the i-type amorphous silicon layer 202 and the n-type amorphous silicon layer 203, a gaseous raw material for forming a deposit film and a gaseous halogen-based oxidizing agent having a property of oxidizing the raw material are vacuumed. It was deposited by mixing and reacting in chamber 120. That is, in the i-type amorphous silicon 202, the SiH filled in the cylinder 101₄The gas is filled in the cylinder 106 from the gas introduction pipe 109 at a flow rate of 30 SCCM.₂The gas was introduced into the vacuum chamber 120 from the gas introduction pipe 111 at a flow rate of 20 SCCM and the He gas filled in the cylinder 107 at a flow rate of 100 SCCM. At this time, the pressure in the vacuum chamber 120 was set to 0.7 Torr by adjusting the opening / closing degree of the vacuum valve 119, and the distance between the gas inlet 111 and the substrate was set to 3 cm. SiH₄Gas and F₂A pale luminescence was strongly observed in the gas mixed region. In the n-type amorphous silicon layer 203, the SiH filled in the cylinder 101₄PH filled in cylinder 104 from gas introduction pipe 109 with a flow rate of 20 SCCM₃/ He (PH)₃F filled the cylinder 106 from the gas introduction pipe 110 with a flow rate of 3 SCCM (concentration 1000 ppm)₂The gas was introduced into the vacuum chamber 120 from the gas introduction pipe 111 at a flow rate of 15 SCCM and the He gas filled in the cylinder 107 at a flow rate of 80 SCCM. The pressure in the vacuum chamber 120 at this time was set to 0.4 Torr by adjusting the opening / closing degree of the vacuum valve 119. In forming each layer, the substrate temperature was set to 250 ° C. The solar cell thus obtained showed a photoelectric conversion efficiency 20% higher than that of the conventional one. (Example 2) FIG. 3 is a schematic configuration diagram of an electrophotographic image forming member according to a second embodiment of the present invention. In the figure, on the Al substrate 300, the light reflection prevention layer 301 (first layer, an amorphous silicon germanium layer whose forbidden band width is controlled by Ge, the thickness is 0.5 μm), and the charge injection prevention layer 302. (Second layer, Amorphous silicon layer doped with B, thickness 0.5 μm), Photosensitive layer 303 (Third layer, Amorphous silicon layer, thickness 18 μm), Surface protection layer and light The absorption increasing layer 404 (4th layer, which is an amorphous silicon carbide layer whose forbidden band width is controlled by C, and has a thickness of 0.1 μm) is laminated and formed. The image-forming member as described above was produced by using a deposit film forming apparatus as shown in Example 1 under the film forming conditions shown in Table 1. The electrophotographic image forming member obtained in this example showed a charging characteristic improved by 22% or more as compared with the conventional product, the number of image defects was reduced by about 10%, and the sensitivity was improved by 18% or more.<img file="JPH0651908B2_D0001.tif" />(Example 3) FIG. 4 is a schematic configuration diagram of a TFT which is a third embodiment of the present invention. In the figure, on the glass substrate 400, an amorphous silicon tank 401 (first layer, thickness 7000 Å), an amorphous silicon layer 402 (second layer, thickness 500 Å) doped with a high concentration of phosphorus, and insulation. Layer 403 (third layer, thickness 1000 Å), gate electrode 404 of Al, source and drain electrodes 405,405'are formed. The above-mentioned TFT was prepared using a deposit film forming apparatus as shown in Example 1 under the film forming conditions shown in Table 2. The TFT produced by this example has an ON / OFF resistance ratio improved by about 15% compared to the conventional one.<img file="JPH0651908B2_D0002.tif" />[Effect of the invention] As described in detail above, since the thin film multilayer structure produced by the method for forming the thin film multilayer structure of the present invention has improved interfacial characteristics, a semiconductor device having excellent characteristics is used as shown in each of the above examples. Obtainable. Further, the method for forming a thin film multilayer structure according to the present invention can save energy and at the same time can easily control the film quality and obtain a deposited film having uniform physical characteristics over a large area. In addition, it is possible to easily obtain a multilayer structure having excellent productivity and mass productivity, high quality, and excellent physical characteristics such as electrical, optical, and semiconductor.

[Simple explanation of drawings]

FIG. 1 is a schematic configuration diagram of a sedimentary film forming apparatus, FIG. 2 is a schematic configuration diagram of a solar cell according to a first embodiment of the present invention. FIG. 3 is a schematic configuration diagram of an image forming member for electrophotographic, which is a second embodiment of the present invention. FIG. 4 is a schematic configuration diagram of a TFT, which is a third embodiment of the present invention. FIG. 5 is a schematic configuration diagram of a deposit film forming apparatus used in a general optical CVD method. 101 ~ 108 ...... Gas cylinder 101a ~ 108a ...... Gas introduction pipe 101b ~ 108b ...... Mass Flometer 101c ~ 108c ...... Gas pressure gauge 101d ~ 108d and 101e ~ 108e ...... Valve 101f ~ 108f ...... Pressure gauge 109,110,111 ...... Gas introduction pipe 112 ...... Base holder 113 ...... Heater for heating the substrate 116 ...... Thermocouple for substrate temperature monitor 118 ...... Hypokeimenon 119 ...... Vacuum exhaust valve 120 ...... Vacuum chamber 123 ~ 125 ...... Gas supply pipe 126a, 126b ...... Light energy generator 127a, 127b ...... Window 200 ...... Glass substrate coated with transparent electrode 201 ...... p-type semiconductor layer 202 ...... Photosensitive layer 203 ...... n-type semiconductor layer 204 ...... Al electrode 300 ...... Al substrate 301 ...... Anti-reflective layer 302 ...... Charge injection prevention layer 303 ...... Photosensitive layer 304 ...... Surface protective layer 405 ...... Al electrode (lease) 404 ...... Al electrode (gate) 405'...... Al electrode (drain) 403 ...... Insulation layer 402 ...... n-type semiconductor layer 401 ...... i-type semiconductor layer 400 ...... Glass substrate