TWI343657B - - Google Patents

Description

1343657 IX. Description of the invention: [Technical field of the invention] The present invention relates to a method for preparing an n+-type polycrystalline germanium film emission layer, particularly a method for preparing a high-temperature process and an atmospheric pressure chemical vapor deposition (Atmospheric) Pressure Chemical Vapor Deposition (APCVD) 'The n+-type diffusion process was developed with a titanium oxide-containing metal compound film and a telecrystalline crystal with a multi-layered polycrystalline stone film. [Prior Art*] The commercially available bismuth-based thin film solar cells are mainly based on Plasma-Enhanced Chemical Vap〇r Deposition (PECVD). A film of amorphous 11 (Alcoa (4) (1) (10)) or Microcrysta (1) neSUic〇n is coated on a substrate such as a glass plate, a metal plate, a stainless steel sheet or a plastic material, and the back electrode material is used. Including gold, silver or tin oxide such as iron oxide

Indium Tin 〇xlde, ιΤ0) and zinc oxide (zinc〇x丨 and Μ) transparent conductive oxide and other materials. The advantage of this low temperature process is that there are many choices for the substrate material: two bombs: However, the disadvantage is that the defects of the stone film material are poor, the light f conversion efficiency is low, and the light stability is improved. In the slurry-enhanced chemical vapor deposition device method, the high-dilution ratio of the stone material is required in the process.

(S 1343657 # In an air environment, the following formula: [H2]/[SiH4]> 15, wherein 'the ratio of [Η2] concentration or flow rate to the [SiH4] concentration or flow rate must be greater than about 15 times. The biggest disadvantages are low growth rate of the film, long process time and high manufacturing cost of the reaction. At present, in the research of thin-film polycrystalline silicon solar cells, various technologies have been developed, which are mainly solid phase crystallization (s〇lid Phase Crystallization (SPC) and Aluminum-Induced Crystallization (AIC). The solid phase crystallization method utilizes the plasma enhanced chemical vapor deposition apparatus method to deposit an amorphous germanium film and then rapidly heat up. And a high temperature annealing process to obtain a typical polycrystalline germanium film of 1 micron to 2 micron (μm) grain size, and another widely studied aluminum metal induced crystallization method (as shown in Figures 5 to 9), Firstly, a layer of aluminum metal film 42 is coated on a substrate 41, and then the plasma-enhanced chemical vapor deposition device is used to coat the metal film 42 with an amorphous layer. The film 4 3 ' is annealed for a long time at an operating temperature of about 575 ° C or less to form a sub-layer 4 4 , and then the plasma enhanced chemical vapor deposition apparatus method or an electron cyclotron resonance microwave plasma is performed. An epitaxial process of a chemical vapor deposition apparatus method (Electr〇n Cyclotron Resonance Chemical Vap〇r Deposition, ECR-CVD), thereby obtaining a polycrystalline germanium film 45. However, the process of the metallization induced crystallization process is complicated and the process is complicated. Long time, its typical grain size is 〇.〗 Micron to 1 〇 micron. 7 ! 343 657 • nm 裎 and electric combustion enhanced chemical gas phase _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Shi Xi film material defects, thin material quality ',

Poor, and the film growth rate is low, the process time is long, and the reaction system = cost ^ is therefore not suitable for the current quality and cost. = Field demand, thin metal crystallization of the metal-induced crystallization method. It takes a long time for complicated processes, so it is also beneficial for low-cost mass production. Furthermore, the non-(10) or microcrystalline film is still a developing technology, and there are unknown variables hidden in it. The general practitioners cannot meet the needs of the user in actual use. SUMMARY OF THE INVENTION The main object of the present invention is to use a high-temperature process and an atmospheric pressure type vapor deposition apparatus method, and a titanium oxide-containing ceramic film containing a titanium-based metal compound film and epitaxially having a polycrystalline germanium film. To develop the η' type diffusion process. A secondary object of the present invention is that the titanium-based metal compound film can be made of titanium dioxide (TiSi2), chaotic (τίΉ), carbonized (TiC), or bismuth bismuth (TiC2) having the same process, purpose, and function. A metal compound such as TiB2) and titanium carbonitride (TiCxNy) is a film material. For the purpose of the above, the present invention is a method for preparing an n+_ type polycrystalline germanium film emissive layer. First, a first aluminum oxide ceramic substrate is selected as a substrate for a polycrystalline germanium thin film solar cell element, and the third oxide is used. The ceramic substrate is covered with a titanium-based metal compound film, and the titanium-based metal compound film is sequentially epitaxially epitaxially formed with a +_-type polycrystalline stone film back surface field (BSF) and - mouth-_ The epitaxial structure formed by the polycrystalline stone thin film light absorbing layer is diffused and deposited by a reactive gas phosphine (Phosphine, PH3) under a high temperature condition by a pressure-type chemical vapor deposition apparatus method. On the p-_ type polycrystalline germanium film light absorbing layer, the phosphorus atom contained in the phosphine is in the mouth __

On the surface of the polycrystalline germanium 4 film light absorbing layer, n+_ type diffusion deposition is performed to form a layer of n+_ type polycrystalline (tetra) film emission which is coated on the P-type polycrystalline germanium film light absorbing layer and less than 1 〇〇〇 thick. Layer (n+_pcsi:p emitter). [Embodiment] Please refer to "Fig. 1 to Fig. 4" for the purpose of the present invention: a schematic diagram of the fabrication process, and the polycrystalline germanium film epitaxial structure of the present invention.

I:: The method of the atmospheric pressure chemical vapor deposition apparatus of the present invention is shown in Fig. 1. Schematic diagram of the n-type polycrystalline germanium film emission layer of X. As shown in the figure, the method for preparing a +-, n-type polycrystalline germanium film emission layer comprises at least the following steps: · exhibiting a plurality of bismuth oxides How much is / / / 1: As shown in Figure 2, first select a thickness of about two U.1 pen meters (mm) $ ! Λ ancient k a p 2 1 as polycrystalline (four) film wide rice trioxide The second crystal is a substrate of a solar cell component, and the trioxane 9 1343657 is coated with a titanium-based metal compound having a thickness of about looo angstroms (A) to 5 angstroms. The film 2 2 is made of a titanium-based metal compound film 2 2 having a polycrystalline thin film seed layer function as a back contact, and the solute crystal is less than or equal to 1 on the titanium-bismuth metal compound film 2 2 . a p+-type polycrystalline silicon film light absorbing layer of a p+-type polycrystalline smectic film (BSF) 2 3 and a thickness of about 15 μm. P_-type polycrystalline germanium film light absorbing layer 2 4 outer surface grain boundary 2 4 2 矽 grain 2 4 1, its size is greater than 1 〇 The titanium-based metal compound film 22 can be made of TiSi2, TiN, TiC, TiB2 or TiCxNy. Metal compound is a film material; (B) atmospheric pressure chemical vapor deposition equipment method (Mm〇spheric

Pressure Chemical Vapor Deposition, APCVD) 1 2 : As shown in Fig. 3, a reactive gas phosphine (PH3) is diffused and deposited on the P-type by an atmospheric pressure chemical vapor deposition apparatus method 3 ' The crystalline film light absorbing layer 24 has a diffusion temperature of about 800 ° C to 1000 ° C, so that the dish atoms contained in the filled hydrogen gas are n+ on the surface of the p__ type ah aa 石 溥 溥 film light absorbing layer 24 _ type diffusion deposition; and (c) n+-type polycrystalline germanium film emission layer i 3 : as shown in FIG. 4, further forming a layer on the p-_ type polycrystalline germanium film light absorbing layer 24 and having a thickness of 5 Å η+·❹晶(四)膜发发层1^43^57

Upc Si:P emiUer) 2 5, wherein the n+-type polysilicon thin film emissive layer 25 is doped with a concentration of ίο! 8 to i 〇 19 phosphorus atoms/cm 3 .

For example, the high-temperature process and the atmospheric pressure chemical vapor deposition device method are combined with the aluminum oxide ceramic material as the substrate, and the titanium-based metal compound film is the back electrode material of the polycrystalline silicon thin film solar cell element, and the polycrystalline silicon is combined On the titanium-based metal compound film of the film seed layer function, the structure of the p+_-type polycrystalline germanium film back surface electric field layer and the P_-type polycrystalline germanium film light absorbing layer is directly epitaxially formed, and an n+_ type diffusion process is developed. Directly obtaining an n+_ type polycrystalline germanium film emitting layer having a thickness of less than 1 Å; and, because of the higher electron hole mobility (Mobimy) and the farther electron diffusion distance (Diffusion Length) of the polycrystalline germanium material And a longer electron tunnel recombination time, which in turn can not only have the high crystal growth rate, high crystal quality, high photoelectric conversion efficiency, and good illumination stability of the polycrystalline silicon thin film solar cell element of the present invention. It can effectively reduce the cost of equipment establishment and simplify the process. In summary, the present invention is a method for preparing a 1 η+· type multi-ruthenium film emissive layer, which can effectively improve various disadvantages of the conventional use, and contains a titanium-based metal compound film and has a multi-layered polycrystalline stone film. The ceramic substrate can be directly obtained by the high-temperature process and the atmospheric pressure vapor deposition equipment method, and the polycrystalline silicon solar cell component can be made to have a high insect crystal rate. The crystallization quality 'high photoelectric conversion efficiency, and good Zhaoguang shift 1343^57 = can also effectively reduce the cost of equipment establishment and make the invention more progressive and practical, and the user must have met Invented the special law to propose a special shot.

The simplified system is more in accordance with the above description, and is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto; & The simple equivalent changes and modifications made are still within the scope of the invention.

1343657 [Simple description of the drawings] Fig. 1 is a schematic view showing the production process of the present invention. Fig. 2 is a schematic view showing the epitaxial structure of the polycrystalline germanium film of the present invention. Fig. 3 is a schematic view showing the method of the atmospheric pressure chemical vapor deposition apparatus of the present invention. Fig. 4 is a schematic view showing the substrate of the n+_ type polycrystalline germanium film of the present invention. Fig. 0 ® Fig. 5 is a schematic view of a substrate. Fig. 6 is a schematic view showing the coating of a conventional aluminum metal film. Figure 7 is a schematic view of a conventional deposited amorphous germanium film. Figure 8 is a schematic view of a conventional seed layer. Figure 9 is a schematic view of a conventional polycrystalline germanium film. [Main component symbol description] _ (part of the present invention) Step 1 1 to 1 3 Oxide oxide ceramic substrate 21 Chinky metal compound film 2 2 ρ+· type polycrystalline germanium film back surface electric field layer 2 3 Ρ--type polycrystalline germanium film light Absorbing layer 2 4 Shixi grain 2 4 1 grain boundary 2 4 2 13 1343657 n+-type polycrystalline germanium film emitting layer 2 5 atmospheric pressure chemical vapor deposition equipment method 3 (conventional part) substrate 4 1 in Lu metal film 4 2 Amorphous germanium film 4 3 seed layer 4 4 polycrystalline germanium film 4 5

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Claims (1)

1343657 Patent application scope: A method for preparing an n+-type polycrystalline germanium thin film emissive layer comprises at least the following steps: (A) selecting a triammonia ceramic substrate, and the trioxide ceramic substrate is coated with a titanium-based metal compound film P+- a BackSurface Field (BSF) and a p-type polycrystalline silicon film light absorbing layer; (B) using an atmospheric pressure chemical vapor deposition apparatus (APCVD), a phosphine (pH 3 ) gas is subjected to n + -type diffusion deposition on the surface of the P-type polycrystalline germanium film light absorbing layer; and (C) is formed on the p - type polycrystalline germanium film light absorbing layer. n+-type polycrystalline germanium film emission layer (n+_pc Si:p emitter). 2) The method for preparing an n+_ type polycrystalline lithi film emission layer according to claim 1, wherein the titanium-based metal compound film is titanium dihydride (TiSh) or titanium nitride (TiN) Metal compounds such as titanium carbide (TiC), titanium diboride (TiB2) or titanium carbonitride (TiCxNy) are thin film materials. 3. The method for preparing an n+_ type polycrystalline germanium film emitting layer according to the invention patent scope, wherein the titanium-based metal compound film has a thickness of 15 S 4 of from Å Å to Å Å. = Please refer to the preparation method of the shot layer mentioned in the patent scope, 曰日夕/#膜fx You A North /, Yin 'The titanium-based metal compound per film # as the back electrode (Back cont: light-weight sub-layer function. And the method for preparing the polycrystalline (tetra) film emissive layer, the second method, the #^ Α Λ 1 ^ - the emulsified aluminum ceramic substrate has a sub-degree of 0.1 mm (mnO). ^.omm., according to the preparation method of the n-ray layer described in the patent application, in the pot, the thickness of the back surface of the p+-type polycrystalline germanium film is less than or equal to 1 micrometer Um) ^Please special · _ η+· :::='In the project, the polycrystalline gamma 2: the twist system! Micron to 15 microns, and its grain size is greater than 1 〇 micron. 8 2 The preparation method of the η+_ type polycrystalline germanium film hair layer described in the first paragraph of the patent scope, wherein the diffusion temperature is 800oC to 1000oC. The η+ type is described in the first item of the patent 1 The method for preparing a thin film emissive layer, wherein the thickness of the η+· type polycrystalline (tetra) film emissive layer is less than 1 〇〇〇. 3657 1 . The method for producing an n+-type polycrystalline germanium film emissive layer according to claim 1, wherein the n+-type polycrystalline germanium film emitting layer is doped with a concentration of 1018 to 1019 phosphorus atoms/cm 3 . 17