TW200535275A - Method and apparatus for forming transparent conductive film - Google Patents

Abstract

Film forming equipment includes a film forming chamber (3) for depositing a transparent conductive film by CVD on a base (1) having an area of 220cm<SP>2</SP> or more, a first gas tube for transporting a first gas including organic metal vapor, a second gas tube for transporting a second gas including oxidant vapor, a gas mixing space (12) for mixing the first gas with the second gas by connecting the first and the second gas tubes, a gas introducing means (10) for introducing a reactive gas mixed in the gas mixing space into the film forming chamber, and an exhaust apparatus (6) for exhausting an exhaust gas from the film forming chamber.

Description

200535275 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for forming a large-area transparent conductive film and the installation of the transparent conductive film. For example, it can be suitably used in thin-film photoelectric conversion devices and crystal display devices. Wait. In addition, in the patent specification A of this case, the terms "crystalline" and "microcrystalline" of a semiconductor thin film may be used in a case where the amorphous state is partially contained if it is generally used on the technical page. [Previous Technology] In recent years, the development of electrical conversion devices using thin films containing crystalline silicon such as polycrystalline silicon and microcrystalline silicon has been in full swing. The purpose of these photoelectric conversions is to develop low-temperature processing to form a good-quality silicon thin film on a low-cost substrate to achieve both low cost and high performance. This type of photoelectric conversion device is expected to be used in various applications such as solar cells and light sensors. In general, it is indispensable to use a transparent conductive film for the manufacture of a photoelectric conversion device. As an example of a photoelectric conversion device, it is known to basically have a photoelectric conversion unit that successively forms a surface electrode composed of a transparent conductive plutonium, a conductive type layer, a crystalline stone-based photoelectric conversion layer, and a reverse conductive layer, including: Photoelectric conversion structure of the back electrode of the reflective metal layer. In general, in order to use the light incident on the photoelectric conversion device more effectively, the surface electrode on the light incident side is provided with a surface unevenness (surface texture) structure to diffuse the light into the photoelectric conversion unit and reflect the metal electrode on the back side. Advanced-step chaos reflection. Further, in order to trap light in the photoelectric conversion unit and effectively use M, a device is known in which a transparent conductive film is inserted between the semiconductor layer and the back surface 99619.d0 &lt; 200535275 electrode. In addition, a device including a transparent conductive film is known as an intermediate layer of a tandem-type photoelectric conversion device having a multilayer structure including a plurality of regions including pn or pin junctions. Conventionally, in a silicon-based thin-film photoelectric conversion device, as a transparent conductive film on a glass substrate, a tin oxide film (for example, a U-type Sn02 film manufactured by Asahi Glass Co., Ltd.) has been widely used as a transparent conductive film on a glass substrate. However, this kind of tin oxide film needs to be treated at a local temperature of more than 500 ° C during the formation of the sun guard, so the cost is higher. As a method for forming a transparent conductive film using a small-scale film-forming device, especially a zinc oxide film, methods such as high-pressure thermal CVD (chemical vapor deposition), vacuum evaporation, sputtering, and low-pressure thermal CVD can be used. However, in high-pressure thermal CVD, the film formation temperature is high, so inexpensive substrates such as glass or plastic films with low heat resistance cannot be used, and when a transparent conductive film is formed on the bottom layer of a semiconductor film, it will occur in the semiconductor film. Defects and impurity diffusion adversely affect device characteristics including the characteristics of the semiconductor film. Under vacuum evaporation ’but the film formation on a large area is difficult

Medium, although it is possible to deposit a transparent conductive film at a lower temperature, it is difficult and the film formation speed is slow. When the sputtering method is used, a transparent conductive film is deposited.

Method (also known as MOCVD (Organic Metal CVD) method). Low-pressure thermal c VD of agent vapor In the conceptual diagram of Fig. 20, 99619.doc 200535275 represents a deposition device using a typical low-pressure thermal CVD method of zinc oxide film disclosed by Wilson W. Wenas et al. In a non-patent document}. . In this film forming apparatus, the inside of the vacuum chamber 4 is a film forming chamber 3 in which the substrate 1 is installed. As the zinc-containing organometal vapor, diethylzinc (DEZ) vapor is supplied to the film forming chamber 3 through a DEZ supply pipe 7 in a state of being mixed with an Ar carrier gas. Similarly, the water (ho) vapor of the oxidant vapor is supplied to the film forming chamber 3 through the outlet tube 8 in a state of being mixed with the carrier gas. Here, the reason why the organometal vapor and the oxidant vapor are introduced into the film formation chamber 3 through separate gas supply pipes 7 and 8 is that when the organometal vapor and the oxidant vapor are transported through the same gas introduction pipe, the The gas introduction tube reacts, and the gas introduction tube will be blocked by the reaction deposit in a short time. Within film formation 3, for example, the glass substrate 1 is heated by the heater 2 and subjected to low-pressure thermal CVD, so that a tin oxide film is deposited on the surface of the glass substrate as a transparent conductive film, and the substrate temperature during film formation is set at 100 ° C ~ 300. Within the range of 〇, the pressure is set at! In the range of 25 t〇rr (133 pa to 3325), the exhaust gas after the reaction from film formation to 3 is discharged from the exhaust port 5 and the exhaust pipe 6 According to this film formation method, when the transparent conductive film is deposited The temperature of the bottom layer is relatively low, so a cheap bottom layer such as glass can be used. In addition, in principle, no ion like that in the case of female shooting is generated, so no damage caused by ions will occur in the substrate or semiconductor layer as the bottom layer. In order to form a large-area transparent conductive film, when using the precedent typically as shown in FIG. 20, the deposited large-area transparent conductive film has a problem in the plane of the sentence. That is, in order to deposit a large-area and uniform 99619.doc 200535275 transparent conductive film by low-pressure thermal CVD, it is necessary to uniformly supply organic metal vapor and oxidant vapor to a large-area bottom layer, and exhaust the gas from there. However, in FIG. 20, since DEZ and H20 are respectively introduced into the film forming chamber 3 by the gas supply pipes 7, 8 respectively, it is difficult to uniformly supply DEZ and H20 on the surface of the substrate 1 with a large area. As a result, it is difficult to maintain the uniformity of the thickness and physical properties of the deposited large-area transparent conductive film. [Non-Patent Document 1] Wilson W. Wenas, Akira Yamada, Makoto Konagai and Kiyoshi Takahashi; &quot; Textured ZnO Thin Film for Solar Cells Grown by Metalorganic Chemical Vapor Deposition '', Jpn. J. Appl. Phys ·, Vol · 30 , No. 3B, March 1991, pp. L441-L443. [Summary of the Invention] In view of the problems of the foregoing precedents, the object of the present invention is to provide a method for forming a large area in low-pressure thermal CVD using an organometal vapor and an oxidant vapor. Method and device for uniform and transparent conductive film. It is also intended to provide a device including the large-area transparent conductive film, such as a large-area photoelectric conversion device or a liquid crystal display device. The film-forming device of the present invention includes a film-forming chamber for depositing a transparent conductive film on a bottom layer having an area of 220 cm2 or more by CVD, a first gas pipe for conveying a first gas containing organic metal vapor, and a vapor containing oxidant A second gas pipe of the second gas, a gas mixing space for combining the first and second gas pipes to mix the first and second gases, and a gas introduction for introducing a reaction gas mixed in the gas mixing space into the film forming chamber Means and exhaust device for exhausting exhaust from film-forming chamber. 99619.doc 200535275 That is, before introducing into the film forming chamber with the bottom layer, by mixing organic metal vapor and oxidant vapor, a large area and uniform transparent conductive film can be deposited on the bottom layer. In addition, by introducing the reaction gas containing organic metal vapor and oxidant vapor into the film forming chamber in a spray shape, the uniformity of a large-area transparent conductive film can be further improved. However, before being introduced into the film forming chamber, if the organic metal vapor is mixed in a pipe heated to, for example, an outer diameter of 1/4 leaf (inner diameter of approximately 4 · 4 mm): water of zinc vapor and oxidant vapor In the case of steam, when the reaction of the organometallic gas and the oxidant vapor in the δ-Hai formulation begins, a transparent conductive film or powder is deposited in the piping, and the piping will be blocked in a short time. Specifically, the piping will be blocked within a period of time required to deposit a zinc oxide film having a thickness of about 200 Å on the glass substrate, and the film cannot be formed. In addition, the piping needs to be heated to prevent liquefaction of ethyl vapor or water vapor. Shu Mingren investigated in detail the reaction strips of organometallic vapors and oxidant vapors. This problem is now a condition that can be obtained in the industrially acceptable time range after the mixing of organometallic emulsifier vapors before the piping is blocked. Specifically, 'the wall temperature control of the space in which the organometal vapor and the oxidant vapor are mixed and the path from which the reaction gas is introduced into the film forming chamber = range' can be used to suppress occlusion of the pipe. In addition, the space for mixing the organometallic steaming and emulsifier vapor and the cross-sectional area of the path for conducting gas to the film-forming chamber from this place are sufficiently increased, that is, the airflow conduction of the pipe is increased to reduce the internal pressure, thereby suppressing the internal pressure. The piping is blocked. Therefore, according to the present invention, the "determined speed" of the transparent conductive film with a large area and uniformity does not affect a substrate or a semiconductor layer as a bottom layer. 99619.doc 200535275 [Effect of the invention]: As mentioned above, according to the present invention, a large-area and uniform uniform transparent conductive film can be formed in low-pressure thermal CVD for the production of organometal vapor and oxidation gas. As a result, a large-area device including a large-area transparent conductive film can be produced, particularly a large-area photoelectric conversion device, and its characteristics can be improved. [Embodiment] First, when a liquid material is used as a raw material for a film-forming gas, it is preferable to vaporize at least one of the liquid materials with a bubble gasifier or a spray gasifier. When DEZ vapor is used as the organometal vapor and H2O vapor is used as the oxidant vapor, DEZ and ZO in the liquid state are vaporized and used. In order to mix this f vapor, it is necessary to make the outlet pressure of the DEZ gasifier approximately equal to the outlet M force of the H2O gasifier. When there is a big difference between the two forces, the low-pressure steam will be pushed back, making the flow unstable or unable to flow out. The outlet pressure of a vapor gasifier is determined by the vapor pressure of the liquid material, so it is difficult to control its outlet pressure. When a vaporizer is used, if the MZ vapor is mixed with the Zao vapor before being introduced into the film forming chamber, the DEZ vapor is lower than the Zao vapor, and there is a problem that the DEZ vapor is pushed back and cannot flow out. When using a bubble gasifier or a spray gasifier, the outlet pressure of the gasifier is approximately determined by the pressure of the carrier gas at a certain time in the pressure of the film forming chamber, so the outlet pressure of the gasifier can be adjusted. In addition, in order to suppress the generation of powder in the gas mixing space 2 (see FIG. 5), the temperature of the gasifier, the DEZ supply pipe 7, and the H20 supply pipe 8 should preferably be as low as possible. For this reason, it is advisable to use a lower temperature foaming gasifier or spray gasifier. Figure 23 is a conceptual diagram of an evaporative gasifier. The heater 26 is used to fill the liquid 99619.doc -10- 200535275 and the groove 27 of the material 28 generates vapor 29 to vaporize the liquid material. The mass of the gasified gas is quantitatively controlled and supplied by the gas mass flow controller 30. This gas Bailey control ^ § 30 also needs to be able to start at the differential pressure between the inlet and outlet at 0.05 MPa. Its price is higher than a negative flow controller that starts with a differential pressure on the general Mpa #. The outlet pressure of the vapor gasifier is determined by the vapor pressure of the liquid material, so it is difficult to control. Therefore, it is not easy to mix the organometallic vapor and the oxidant vapor before entering the film forming chamber. Figure 24 is a conceptual diagram of a bubble gasifier. The Ar carrier gas is passed into the liquid material 28 to generate bubbles 33, thereby vaporizing the liquid material. Ar is supplied while the flow is controlled by the gas mass flow controller 34. This gas mass flow controller 34 is a general mass flow controller which is started at a differential pressure of 0.05 MPa or more. The tank 27 is set in the thermostatic tank 32 and the temperature thereof is controlled to be constant. Ar is mixed with the gasified gas and flows out from the outlet of the bubble gasifier. The gas flow rate gasified by the bubbling gasifier is determined by the Ar flow rate, the temperature of the liquid material, the liquid level height, etc., and it is difficult to control quantitatively. From the reduction in the total weight of the groove 27 and the liquid material 28 measured by the weight gauge 31, the approximate value of the vaporized liquid material can be determined. The outlet pressure of the bubble gasifier is roughly determined by the pressure of the carrier gas and can be controlled. Therefore, before entering the film forming chamber, an organometal vapor and an oxidant vapor may be mixed. In Fig. 25, '(a) is a conceptual diagram of the entire spray gasifier, and (b) is an enlarged conceptual diagram of the mixer 36 included in the more advanced, high-tech, high-tech, high-tech, low-tech (36). While supplying the Ar carrier gas flow rate by the gas mass flow control 34, the liquid material flow rate is controlled by the liquid mass flow controller 35 while supplying it, and the mixer is combined to vaporize it. As shown in Fig. 25 (a), the vice coordinator 3 supplies 99619.doc -11-200535275 for Ar gas. The liquid material is supplied as a mist-like liquid material 40 through a micro hole 39 through a liquid material supply pipe 38. The atomized liquid material 40 is gasified by the strongly flowing Ar gas, and is then led out by the gasified gas supply pipe 41. The outlet pressure of the spray gasifier is roughly determined by the pressure of the carrier gas, so it can be controlled. Therefore, 'the organic metal vapor and the oxidant vapor can be mixed before entering the film forming chamber. In addition, since all the liquid materials passing through the liquid mass flow controller 35 are vaporized, quantitative control of the vaporized gas can be performed. In addition, the spray gasifier is more expensive than the bubble gasifier, but it is cheaper than the evaporative gasifier. • The conceptual diagram of FIG. 5 shows a method for forming a transparent conductive film according to an embodiment of the present invention. In this figure, a film-forming chamber 3 of a substrate 1 is arranged inside the vacuum chamber 4. Diethyl zinc (DEZ) vapor containing organic metal vapor is supplied to the gas mixing space 12 in a state mixed with an Ar carrier gas, and water (KUO) vapor of an oxidant vapor is mixed with an Ar carrier gas It is supplied to the gas mixing space 12, thereby preparing a reaction gas containing deZ, h2O, and Ar in the gas mixing space 12. An example of the piping near the 'gas mixing space' in the schematic diagram of FIG. 21. Paralysis In this figure, the area surrounded by the dotted line at the confluence position of the DEZ supply pipe 7 and the Η20 supply pipe 8 is the gas mixing space 12. The DEZ supply pipe 7 is heated by the heater 71, and the HW supply pipe is heated by the heater §1. The reaction gas system prepared in the gas mixing space J 2 is guided by the reactor body pipe 丨 丨 to the film forming chamber 3. Although the confluence position of DEZ radon and steam is a gas mixing space 2, in fact, there is a certain degree of h2O vapor in the DEZ supply pipe 7 due to diffusion. There is some kind of H2O supply in 8 Degree of DEZ vapor. Therefore, ZnO powder can be generated in the DEZ supply pipe 7 and the He supply pipe 8. 99619.doc 12 200535275 Compared with piping, if a valve with low airflow conductivity is arranged near the gas mixing space 12 ', the valve will be blocked by the generated powder in a short time. Therefore, “the gas mixing space 12 is provided on the upstream side of the DEZ supply pipe 7” The initial DEZ supply valve 24 is preferably at a distance of 0.3 m or more from the gas mixing space 12 (distance A in FIG. 21), A distance of 1 η or more is more ideal. Similarly, the initial supply valve 25 provided on the upstream side of the h2O supply pipe 8 from the gas mixing space 12 is preferably at a distance of 0.3 m or more from the gas mixing space 12 (distance B in FIG. 21), and more preferably at a distance of 1 m or more. As ideal. • The density of the private 0 in the DEZ supply pipe 7 can be calculated using the following diffusion equation: D · a2 NH / a x2-k · nh · Nd = 0 (Equation 1) Here, D is the diffusion constant of H20, NH Is the molecular number density of H20, x is the distance from the gas mixing space 12 along the DEZ supply pipe 7, k is the reaction rate constant of DEZ vapor and H20 vapor, and ND is the molecular number density of DEZ vapor. Solving formula 1 gives the following formula: NH = NH0 · exp [-/ ~ {k · ND / (NH0 · D)} · X] (Equation 2) W Here, NH0 is H20 in the gas mixing space 12 Molecular number density. The graph in FIG. 22 shows an example of the calculation result of Expression 2. The horizontal axis of this curve represents the distance X from the mixing space 12 along the DEZ supply pipe 7, and the vertical axis represents the relative density of H20 at the distance X when the H20 concentration in the gas mixing space 12 is 1. At this time, the partial pressure of the DEZ vapor in the gas mixing space 12 is 75 Pa, and the partial pressure of the H20 vapor is 75 Pa. It is assumed that the diffusion rate D of H20 estimated from the molecular weight is D = 0.01 m2 / s, and the reaction rate constant k estimated from the film-forming speed of ZnO is k = 1.3xl (T28m3 / s. 99619.doc -13- 200535275). · For the concentration of h20 in the gas mixing space 12, when the distance 乂 is greater than 0.3 m, the relative concentration of Ηβ is less than 1%, and is less than 1 ppm at χ =; ι _ temple. That is, as described above, mixed by the gas When the distance A from the space 12 to the DEZ supply valve 24 is more than 0.3 m, it can suppress the generation of Zn0 powder and prevent the resistance of the valve. It is more ideal when it is more than 1 m. In the H2O supply pipe 82DEZ, the degree is also correct. The distance decreases logarithmically, so the distance A from the gas mixing space 12 to the H2O supply valve 25 is more than 0.3 m, and more preferably, it is more than im.

The reaction gas prepared in the gas mixing space 12 is supplied to the film formation chamber 3 via a reaction gas pipe 11, a diffusion phase 9, and a reaction gas formed by the shower plate 10. The reaction gas is sprayed from a plurality of holes provided in the shower plate 10 in a shower shape, and is uniformly supplied into the film forming chamber 3. The wall surface of the gas mixing space 2 and the wall surface of the reaction gas path (reaction gas piping U, the diffusion box 9, and the shower plate 10) are controlled by a wall surface heater &quot;. The glass substrate i is heated by the heater 2 to perform low-pressure thermal CVD, and a zinc oxide film as a transparent conductive film is deposited on the substrate surface. As the heater 2, for example, an armored heater can be used. The exhaust gas is discharged by a pump (not shown) through an exhaust port 5 and an exhaust pipe 6. The capacitance pressure gauge and the capacitance variable valve (not shown in Fig. 5) can be used to keep the pressure in the vacuum tank 4 constant. When depositing the oxide film, for example, the pressure in the vacuum tank 4 can be set to 5 to 200 Pa, the substrate temperature can be 100 to 300 t, the dez vapor flow rate can be 10 to 1000 seem, and the H2O vapor flow rate can be 10 to 100. 〇sccm and &amp; flow range 100 ~ 10000 seem. In the embodiment shown in FIG. 5, not only the wall surface of the gas mixing space η outside the vacuum tank 4 but also the wall surface of the reaction gas passage 9 and ι〇 protruding in the vacuum tank 4 are 99,619.doc-14.200535275. temperature control. On the other hand, ^ ^ ^ Α In Comparative Example 1 or 3 described succinctly, in the reaction gas path, only the outer part of the vacuum tank and the part are heated to about 80 ° C. The gas mixing space or the reaction gas path When the temperature of the wall surface of the road is too high, everywhere, organometallic vapors and oxidants vaporize oxygen, and milk reacts, and a transparent lightning film or powder is deposited to cause occlusion. Also, gas, “industrial &amp; body mixing space Or, if the temperature of the wall surface of the reaction gas path is too low, it is difficult to maintain the pressure of the organic metal vapor and the oxidized W vapor of the car, and liquefaction may occur in the worst case. To avoid this, control the wall heater 13 to mix the gas

The temperature control of at least-part at least-part of the wall surface of the concrete working room and the reaction gas path is ~~ ⑽. c, It is preferably controlled to 50 ~ 8 (TC, and preferably controlled in the range of 55 to 6 generations. As the surface heater 13, for example, a resistance heating type heater (bell-mounted teaching device: belt heater) , Silicone rubber heater), infrared heater, heating medium circulation heater (heater that circulates heating oil or water and other fluids), etc. When the cross-sectional area of the gas mixing space or reaction gas path is small, the air flow mobility will change. Compared with the pressure in the film forming chamber, the pressure in the gas mixing space or the reaction gas path will become very high. At this time, when DEZ and HA are mixed in the gas mixing space, the film and powder are generated in the piping and the Occlusion occurs for a short time. In order to avoid occlusion of the piping, in the present invention, the cross-sectional area of the gas flow between the gas mixing space and the reaction gas path is set to 28 mm2 or more, preferably 78 mm2 or more, and most preferably 300 mm2 or more. Gas When the mixing space or the reaction gas path is a cylindrical pipe, its inner diameter is set to 6 mm or more, preferably 10 mm or more, and more preferably 20 mm or more. In order to suppress the blockage caused by the precipitated powder, the gas is blocked. Mixed space The reaction speed of the reaction gas path is 99,619.doc -15- 200535275 degrees, which is less than 50 times the reaction speed in the film forming chamber. When the force in the film forming chamber is 200 Pa, it is necessary to control the pressure in the pipe to ⑽⑽ t 〇rr) or less. At this time, when a transparent conductive film with a thickness of 1 is deposited with a pipe inner diameter of 6 mm, more than 50 batches of film can be formed. In addition, in order to be easily cleaned even when the gas mixing space or the reaction gas passage is blocked, it is preferable to provide a joint that can be lowered and reinstalled at least in a part of the boundary between the gas mixing space and the reaction gas passage. As the joint, it is preferable to use a joint capable of sufficiently performing vacuum sealing and having chemical resistance to organic metal vapor and oxidant base gas. Specifically, it is preferable to use a metal sealing joint, for example, a joint using stainless steel as a sealing material. In addition, it is preferable to use a joint of fluoro rubber or iron gas dragon (registered trademark) using o f ring joint m sealing material. X ’〇 ring joint—a kind of fastening joint⑽ It can be easily removed and reinstalled without using tools, so it is easy to clean the gas mixing space or the reaction gas path. The transparent conductive film is not limited to a zinc oxide film. Similarly, the present invention can also be applied to other transparent conductive films which can be formed by the low barrier of organic metal vapor and oxidant vapor ... CVD. In addition, the organometallic vapor is desorbed in the DEZ gas. As an example of an organometallic vapor other than DEZ, oxomethyl zinc vapor is used, but other organometallic vapors that can be used to form a transparent conductive film can be used in the same manner. The oxidant vapor of the present invention is not limited to 0 vapor. Examples of oxidant vapors other than Η20 include oxygen, carbon dioxide, carbon dioxide, lice, nitrogen dioxide, sulfur dioxide, dinitrogen pentoxide, alcohols ((〇Η)), _ (R ( C0) R,), ethers (ROR,), aldehydes (r (COH)), 99619.doc -16- 200535275 3), and amines (RCO) such as sulfoxides (R (SO) R,) x (NH3_x), X = 1 and the same can be used for any other oxidant vapor which is effective for the shape of Qianming conductive film. Here, R &amp; R represents an alkyl group. The spirit of the present invention is not limited to ^ A] •. As an example of a carrier gas other than tritium, I use other rare gases (He, Ne, Kr, Xe, Rn), nitrogen, chlorine, etc. In addition, a gas that is substantially inert to organometallic vapors and oxidant vapors can be used.

The substrate of the present invention is not limited to glass hiding plates. Examples of substrates other than glass substrates include metal plates, gold, organic films, and the like, as long as they can withstand the temperature at the time of film formation and have low outgassing. In addition, the substrate need not be a substrate of the present invention, and may be a substrate having an irregular surface such as a curved surface. As the size of the substrate, the present invention is preferably applicable to the case where the surface area of the substrate of the transparent conductive film that can be deposited is 220 cm2 or more, especially 1300 cm or more. In Comparative Example 2 and Comparative Example * described later, compared with the central region of the substrate, regions having a film thickness uniformity of 95% or more can only be achieved to about 220 cm2 and about 1300 cm2, respectively. That is, a transparent conductive film cannot be uniformly formed on a substrate having a film formation area larger than this. On the other hand, in Example 1 of the present invention described later, compared with the central region of the substrate, a region having a film thickness uniformity of 95¾ or more can be enlarged to about 9580 cm2. In order to increase the conductivity of the transparent conductive film, in addition to organometal vapor and oxidant gas, it is quite effective to mix a gas containing a Group 3 element. In the device suitable for the transparent conductive film for improving the conductivity, the resistance loss can be reduced. As a gas containing a Group 3 element, for example, a gas containing diboron, tri-99619.doc 200535275-based boron, difluoride, or tri-f-based aluminum can be used. In order to prevent the transparent conductive film from being formed in the back surface of the substrate, the glass substrate 4 is used. In the embodiment shown in FIG. 5, the substrate 2 is in contact with the heater 2. Making the back surface of the substrate = prevent = instead of bringing the back surface of the substrate into contact with the heater may be used. For example, when using an all-metal plate or stone plate with good thermal conductivity as its plate-like member, the temperature of the substrate is uniform, and even: the thickness and physical properties of the transparent conductive film on the substrate are ideal. .

In the embodiment shown in Fig. 5, as the heating means of the substrate, although a heater is used as an example, a cast-in heater, an infrared lamp heater, a heating medium circulation heater, etc. may be used in the same manner. Fig. 15 is a schematic sectional view showing a photovoltaic converter according to another embodiment of the present invention. In the production of this photoelectric conversion device, an oxide film is formed on the glass substrate 16 as the surface electrode 17 using the film forming device of FIG. 5. On the surface electrode 17, a first thin-film semiconductor photoelectric conversion unit 18 with a pin junction and a second thin-film semiconductor photoelectric conversion unit 19 with a pin junction are formed by a plasma CVD method. On the second unit 19, a metal layer is formed as the back electrode 20 by a coin shooting method. In this photoelectric conversion device, light incident from the glass substrate 16 side is subjected to photoelectric conversion by the first photoelectric conversion unit 18 and the second photoelectric conversion unit 19 which constitute a hybrid structure. The first photoelectric conversion unit 18 is composed of a first p-type semiconductor layer 18a doped with amorphous carbon carbide doped with B (rotten), a first true semiconductor layer 18b with amorphous silicon, and doped with P (phosphorus). It is composed of the first n-type semiconductor layer 18c of microcrystalline silicon. The second photoelectric conversion unit 19 is composed of a second p-type half of B-doped microcrystalline stone. 99619.doc -18- 200535275 / conductor layer 19a, a polycrystalline second true semiconductor layer ⑽, and a p-doped M is composed of the first n-type semiconductor layer J 9c of silicon. The reason for using the polycrystalline stone in the second true semiconductor layer is that the polycrystalline stone can absorb light with a longer wavelength than the amorphous phase. Therefore, the long wavelength light that is not completely absorbed by the first true semiconductor layer 18b can be used. It is absorbed by the second true semiconductor layer 19b, which can increase the Pmax of the photovoltaic device.

In the surface electrode 17, 'the larger the thickness, the lower the sheet resistance, thereby the' resistance loss of the photoelectric conversion device will be reduced ... the larger the thickness of the surface electrode ', the larger the surface unevenness, and incident on the photoelectric conversion The light of the device is "radiated" to extend the length of the optical path, which can increase the short-circuit current of the photoelectric conversion device. However, when the 'surface electrode 17 is too thick, the light absorption loss of the surface electrode π will increase and Ise will decrease. For this reason, the thickness of the transparent conductive film on the material surface exists in a suitable range, preferably ㈣ ′, more preferably ⑴_ ′, and most preferably 15 to 25 ㈣. In the embodiment shown in FIG. 15, the amorphous silicon anionite fossil is used as the core of the p-type semiconductor layer, but the present invention is not limited to this. In order to generate a sufficient diffusion potential for the first photoelectric conversion unit 18, b or M doped amorphous silicon or a wide band gap amorphous silicon alloy (amorphous silicon carbide, amorphous oxide, Amorphous nitride nitride eve) and so on. In particular, in order to reduce the light absorption loss of the p-type semiconductor layer 18a, it is preferable to use an amorphous chopped alloy with a wide band gap. As the -n-type semiconductor layer 18c ', p-doped amorphous silicon can also be used. In the implementation shown in FIG. 15, although the true semi-sacral layer is made of amorphous stone and polycrystalline silicon, microcrystalline stones of other non-single crystal semiconductors can also be used. Non-99619.doc -19- 200535275 crystalline Shi Xi alloy, microcrystalline Shi Xi alloy, polycrystalline Shi Xi alloy, etc. As the shixi alloy, for example, a shixi alloy that is one of the elements of carbon, nitrogen, and oxygen is preferably used. In the embodiment shown in FIG. 15, although a silicon-based thin film • rhenium conductor is used in the photoelectric conversion device, a compound semiconductor such as copper indium, copper indium gallium, selenium, cadmium sulfide, and tellurium sulfide can also be used. In the photoelectric conversion device of the embodiment shown in Fig. 15, although a transparent glass substrate, a transparent conductive film, a semiconductor layer, and a metal layer are laminated in this order, the present invention is not limited to this. For example, the present invention is also applicable to, for example, a photoelectric conversion device that is laminated in the order of an opaque substrate, a semiconductor layer, and a transparent conductive film. In addition, the photoelectric conversion unit included in the photoelectric conversion device is not limited to a two-layer laminated photoelectric conversion unit as shown in FIG. 15, and the present invention can also be applied to a photoelectric conversion device including an arbitrary number of photoelectric conversion units of one or more stages. Fig. 19 is a cross-sectional view showing a large-area thin-film photoelectric conversion device according to still another embodiment of the present invention. The large-area thin-film photoelectric conversion device has a structure of an integrated photoelectric conversion module in which a plurality of photoelectric conversion cells divided into a small area are connected in series to each other on a glass substrate. Each photoelectric conversion cell line uses the film-forming device of FIG. 5 to sequentially execute the surface electrode of a transparent conductive film formed on a glass substrate, the semiconductor portion of one or more thin-film semiconductor photoelectric conversion units laminated, and the film formation of the back electrode layer. Formed by. The integrated thin-film photoelectric conversion module 1001 of FIG. 19 is a pin-bonded structure consisting of a surface electrode layer 103 of a transparent conductive film and a true semiconductor layer containing amorphous silicon, which are successively laminated on a glass substrate 102. The structure of a photoelectric conversion unit 104a, a second photoelectric conversion unit 104b formed by pin bonding of a true semiconductor layer containing crystalline silicon, and a back electrode layer 106. 99619.doc -20- 200535275 As shown in FIG. 19, the integrated thin-film photoelectric conversion module ι01 is provided with first and second separation grooves 121 and 122 and a connection groove 123. The first and second separation grooves 121, 122, and the connection groove 123 are parallel to each other and extend in a direction perpendicular to the drawing surface. In addition, the power generation region of one photoelectric conversion cell 110 is a region between the first and second separation trenches 121 and 122. The first separation grooves 121 divide the surface electrode layer 103 in correspondence with the photoelectric conversion cells 110, respectively. That is, the first separation trench 121 electrically separates adjacent surface electrode layers 103 from each other. Similarly, the second separation trench 122 is divided into a first photoelectric conversion unit 104a, a second photoelectric conversion unit 104b, and a back electrode layer 106 corresponding to the photoelectric conversion cells 110 respectively. That is, the second separation trench 122 electrically separates the back electrode layers 106 from each other between adjacent photoelectric conversion cells 110. The connection groove 123 is provided between the first separation groove 121 and the second separation groove 122, and is used to divide the first photoelectric conversion unit 104a and the second photoelectric conversion unit 104b. This connection groove 123 is embedded in a metal material composing the back electrode layer 106 for electrically connecting the back electrode layer 106 of one of the adjacent photoelectric conversion cells 110 and the surface electrode layer 103 of the other cell in series. That is, the connection trench 23 and the metal material embedded in the trench can electrically connect the photoelectric conversion cells 110 placed on the glass substrate 102 in series with each other. In the integrated thin-film photoelectric conversion module thus formed ', since the small-area photoelectric conversion cells are connected in series, the power generation current of the module is limited by the photoelectric conversion cell having the smallest current generation. Therefore, in order to make the power generation current of the majority of cells contained in a module uniform, it is particularly important to form a surface electrode layer of a transparent conductive film with a uniform film thickness distribution using the film forming apparatus of FIG. 5. The oxide film of the transparent conductive film formed by the film forming apparatus of FIG. 5 can also be used as a back surface reflective layer between the semiconductor layer and the back surface electrode layer of the photoelectric conversion device. The back surface reflection layer is too thin, and the reflectivity is not sufficient. When the back surface reflection layer is too thick, the absorption loss of the back surface reflection layer will increase, so its thickness is suitable. As the semiconductor layer of the photoelectric conversion device, an amorphous stone or a crystalline stone is used, a metal layer is used for the back electrode layer, and a transparent conductive film of zinc oxide is used as the back reflective layer between the semiconductor layer and the metal layer. The thickness of the back reflective layer is preferably in the range of 10 to 150 nm, more preferably in the range of 305 to 30 to 120 nm, and most preferably in the range of 60 to 90 run.

The oxide film of the transparent conductive rhenium formed by the film-forming device of Fig. 5 can also be used as an intermediate layer in a tandem-type photoelectric conversion device having a plurality of photoelectric conversion units. For example, a zinc oxide film of a transparent conductive film may be provided as an intermediate layer between the _th photoelectric conversion unit 18 and the second photoelectric conversion unit 19 of the photoelectric conversion device of FIG. 15. This kind of intermediate layer is too thin. If the light reflectivity and light scattering properties are not sufficient, the absorption loss of the material layer will increase, so there exists a desirable thickness range. When the true semiconductor layer 18b of the first photoelectric conversion unit uses amorphous silicon, the intermediate layer uses an oxide film, and when the true semiconductor layer 19b of the second photoelectric conversion unit uses polycrystalline silicon, the thickness of the intermediate layer is preferably at 2 to 150 nm, more preferably 10 to 100 nm, and most preferably 30 to 60 nm. In the embodiment shown in Fig. 15, although two pin junctions are overlapped, the present invention is of course applicable to a photoelectric conversion device including more than one pin junction, nip junction, pn junction, or np junction. [Examples] Hereinafter, examples of the present invention will be described in detail together with comparative examples. 99619.doc -22- 200535275 (Comparative Example 1) In the conceptual diagram of Fig. 1, as Comparative Example 1, an example of a conventional film forming apparatus for a transparent conductive film using low-pressure thermal CVD is shown. In this film forming apparatus, the inside of the vacuum chamber 4 is a film forming chamber 3 on which a substrate 丨 is provided. As the zinc-containing organometal vapor, diethylzinc (DEZ) vapor is supplied to the film forming chamber 3 through a DEZ supply pipe 7 in a state of being mixed with a carrier gas. In Comparative Example U, an evaporative gasifier was used. The DEZ supply pipe 7 is a stainless steel pipe with an outer diameter of 1/4 inch (inner diameter of about 4.4 mm). In order to increase the vapor pressure of the DEZ vapor to prevent liquefaction, a part of the DEZ supply pipe 7 is heated by a heater 71 to about 80. 〇. Water (HA) vapor of lice agent vapor is also supplied to the film forming chamber 3 through the H2O supply unit 8 in a state of being mixed with the Ar carrier gas.供应 &quot; Supply tube 8 is also a stainless steel tube with an outer diameter of 1/4 inch (inner diameter of about 4.4 mm). In order to increase the vapor pressure of the private steam to prevent liquefaction, a part of the H2O supply pipe 8 is heated to about ⑽ with a heater 8. The glass substrate 1 is heated by the heater 2 to perform low-pressure thermal CVD, and a zinc oxide film is deposited on the surface of the glass substrate surface 1 as a transparent conductive film. As heater 2 is an armored heater. The exhaust gas is discharged by a pump (not shown) through an exhaust port 5 and an exhaust pipe 6. The capacitance pressure gauge and the variable capacitance valve not shown in the figure can be used to keep the pressure in the vacuum tank 4 constant. When depositing a zinc oxide film, for example, the pressure in the vacuum tank 4 can be set to 100 Pa, the substrate temperature can be 20 ° (Γ (:, DEZ vapor flow rate 500 seem, H2O vapor flow rate 500 seem), and Here, the DEZ supply pipe 7 and the H20 supply pipe are added to 2000 sccm 0 (Comparative Example 2). The schematic plan view of FIG. 2 is used as Comparative Example 2, and the film forming apparatus of FIG. Thickness distribution at the time of film. The value of 99619.doc -23- 200535275 in Figure 2 represents the contour line of the film thickness in ^^ units. In addition, the thickness of the transparent conductive film is determined by measuring the reflectance of the transparent conductive film on the glass substrate. The thickness of the film is determined by the change in reflectance caused by interference. This measurement and analysis is performed using a wafer mapping system made by Sendek Instruments. As shown in Figures 1 and 2, it is equivalent to a DEZ supply tube. 7 and the private 0 supply tube 8 ^ The film thickness is large, and the film thickness decreases sharply when shifted to the periphery. Also, there is no film deposition at the peripheral portion of the substrate. It is in accordance with the film thickness in the central area of the substrate. Ratio, more than 75% of the film thickness area, 580% of the substrate area of 5.8% cm2 '| more than 95% of the film thickness area is only 2.2% of the substrate area of 220 cm2. Therefore, the reaction between DEZ and h2〇 is only carried out near the directly below the dez supply pipe 7 and HA supply pipe 8 to make the film thickness distribution It becomes extremely bad. In Comparative Example 20, since there is a completely non-film-deposited area on the peripheral edge of the substrate, the transparent conductive film cannot be applied to the surface electrode of a large-area photoelectric conversion device. (Comparative Example 3) Figure The conceptual diagram 3 is another comparative example 3, showing another example of a conventional film-forming apparatus using a low-voltage thermal cVD. Similar to the comparative example in FIG. 丨 (Similarly, in FIG. 3, the inside of the vacuum tank 4 is also For the film forming chamber 3, the glass substrate i can be heated by the heater 2. However, in FIG. 3, the mixed gas system of OEZ and Ar is temporarily supplied into the diffusion box 9 by the DEZ supply officer 7, and the hole of the shower plate It is supplied to the film-forming chamber 3 in a spray shape. The DEZ supply pipe 7 is a stainless steel pipe with an outer diameter of 1/4 called ~ (inner diameter of about 4 · 4 mm). Part of the DEZ supply pipe 7 is a heater 71. It is heated to about 80 ° C. The mixed gas system of HW and Ar is supplied by two Ηβ arranged opposite to each other on the opposite wall surface of the vacuum tank 4. The supply pipe 8 is supplied to the film forming chamber 3. The H20 supply pipe 99619.doc -24- 200535275 8 is also a stainless steel pipe with an outer diameter of 1/4 pair (inner diameter of about 4.4 mm). A part of the h20 supply pipe 8 is also The heater 81 is heated to about 8 (rc.) The glass substrate 丨 is heated by the heater 2 and subjected to low-pressure thermal CVD. A transparent conductive film of zinc oxide is deposited on the surface of the glass substrate 丨. In this comparative example 3, oxide was deposited. The gas force and gas flow rate of the zinc film daily guard were the same as those in Comparative Example 1. (Comparative Example 4) The schematic plan view of Fig. 4 is Comparative Example 4, and the thickness distribution when the zinc oxide film was formed on the 1 mxl m glass substrate 1 by the film forming apparatus of Fig. 3 was used. The numerical values in FIG. 4 represent contour lines of film thickness in μm units. Comparing this comparative example 4 of FIG. 4 with the comparative example 2 of FIG. 2, the area where the transparent conductive film is deposited on the glass substrate is wider. However, in the case of Fig. 4, the thickness of the transparent conductive film is still large in the central region of the substrate, and the film thickness gradually becomes thinner as it moves toward the periphery of the substrate. And the center of the region with a larger film thickness is shifted to the slightly right side of the substrate, and it can be seen that the film thickness becomes larger near the exhaust port 5 side in FIG. 3. This is because the airflow is deviated to the right side of the substrate 1 in the exhaust direction. Compared with the film thickness in the central area of the substrate, a film thickness area of more than 75% is 3860 cm2 of 386% of the substrate area, and a film thickness area of 95% or more is 13 10% of the substrate area. As shown in Comparative Example 6 described later, when this transparent conductive film is applied to a surface electrode of a large-area photoelectric conversion device, only a very low photoelectric conversion characteristic can be obtained, and the film does not have sufficient uniformity suitable for a large-area device. Film thickness distribution. (Comparative Example 5) In Comparative Example 5, in the film-forming apparatus of Fig. 3, a reaction gas of mixed DE grave gas, HA gas, HA vapor, and Ar was supplied to the βEζ supply pipe 7. In this case, 99619.doc -25- 200535275 The shape of the DEZ supply pipe 7 is blocked by the precipitated powder in about 1 to 2 minutes, and a transparent conductive film cannot be formed on the substrate 1. At this time, when the pressure of the film forming chamber 3 is about 100 Pa ', when the total flow rate of DEZ and Ar is set to 10,000 sccm, the pressure in the DEZ supply pipe 7 reaches about 5000 Pa.

When the raw material gas is fully supplied, the reaction speed of DEZ and H2O is proportional to the partial pressures of DEZ and gas, and therefore the reaction speed is proportional to the second power of the full pressure. In the case of Comparative Example 5, the pressure in the gas mixing space is 50 times the pressure in the film forming chamber. Therefore, in the gas mixing space, the reaction proceeds at a speed of 2500 times compared to the film forming chamber. Occurrence of occlusion due to transparent conductive film or powder inside the body. And because the inner diameter of the tube is as small as about 4.4 mm, as the powder is formed, the gas path becomes gradually narrower, and the pressure becomes larger and larger. When the reaction proceeds in a short period, the piping will be blocked in a short time. In Comparative Example 5, since a vaporizer was used, the 'DEZ vapor pressure was lower than the h20 vapor pressure at the same temperature, and the Mζ vapor and the h20 vapor could not be closely mixed. However, when observing the closed piping carefully, it was found that the mz is close to the piping measured by the gasifier, and "close to the piping measured by the gasifier." Therefore, it is believed that the DEZ vapor has a tendency to be pushed back by the Η &quot; vapor. (Example 1) Zinc oxide was formed as a film according to the present invention using the hafnium-forming apparatus of Fig. 5. In the first embodiment, the cylinders, and the faucets are used in an emulsified state, and the wall temperatures of the gas mixing space 12 and the reaction gas passage are controlled to 6 (rc. In addition, in the first embodiment, The distance between the piping in Figure 21 is 015 m. The reaction gas piping U uses a cylindrical tube with an inner diameter of about 25 ugly larger than that in the past, and its-part is connected by NW25 type fastening joint (not shown). The diameter is sufficiently large, 99619.doc -26- 200535275, so the airflow conductivity is increased, the pressure of the gas mixing space 12 and the reaction gas path is reduced, so that the occlusion of the tube can be suppressed. And as long as the fastening joint is removed, it can be easily The powder or transparent conductive film in the tube is cleaned on the ground. The result of using the film-forming device of Example 1 is' 100 Pa in the film-forming chamber 3 and pressure 300 Pa in the gas mixing space, even if it is performed. For a total of more than 300 hours of film formation, the piping will not be blocked. That is, Example 丨 can be said to be a film forming method that can be used industrially. (Example 2) The schematic plan view of FIG. 6 is Example 2. In the figure, the device is formed on a glass substrate 1 of 1 mx 1 m. Thickness distribution when the zinc film is formed. When a zinc oxide film is formed on a glass substrate 1 of 1 mxl m, the size of the shower plate 以 is, for example, 1.1 mxl.lm. Also, during film formation, The pressure is 100 Pa, the substrate temperature is 20 (rc, the DEZ vapor flow rate is 50 °), the H20 vapor flow rate is 50 sccm, and the flow rate is 2000 sccm. The values in FIG. 6 are expressed as / ^ 111 The unit indicates the contour line of the film thickness. Except for the four corners of the substrate, a uniform film thickness distribution can be obtained. The right side of the film forming device in Fig. 5 has an exhaust port 5, which is close to the right side of the exhaust port 5 in the four corners of the substrate Compared with the two corners, the area with a smaller film thickness is slightly wider in the two corners on the far left side. Compared with the film thickness in the center area of the substrate, more than 75% of the film thickness area is 98.6% to 9860 cm2 of the substrate area. The area with a film thickness of 95% or more is 95.8% of 9580 cm2 of the substrate area. Therefore, in Example 2, it can be seen that the uniformity of the film thickness is significantly improved as compared with Comparative Examples 2 and 4. In addition, the transparent conductive film was investigated. As a result of the characteristics, it is suitable for a light transmittance of more than 80% (wavelength of 400 n). m ~ 100nm), ΐ5Ω / 〇99619.doc -27- 200535275, the characteristics of sheet resistance below 1035275 and haze rate above 10% can be obtained in the range of 5 ~ 200 Pa of film forming chamber pressure. And in the pressure of the film forming chamber within this range, a fast film forming speed of 1 nm / s or more in the thickness direction can be obtained. Also, the so-called haze rate is an index for optically evaluating the surface unevenness of a transparent substrate, (Diffusion transmittance / total light transmittance) χ 100 (%) (JIS K7136) 〇 Film formation to &gt; When the force is lower than 5 Pa, the film formation speed will be lower than 1 nm / s. Film formation time will be prolonged, and manufacturing costs will increase. In addition, in order to reduce the pressure of the film forming chamber, a pump having a high exhausting capacity is required, so the manufacturing cost will increase. On the other hand, when the pressure of the film forming chamber is higher than 200 Pa, characteristics suitable for the photoelectric conversion device as described above cannot be obtained. In addition, when the pressure of the film forming chamber is less than 2000 Pa, when the inner diameter of the gas mixing space is 25 mm, the pressure in the gas mixing space is less than 300 Pa. It is generally maintained regardless of the pressure of the film forming chamber.疋 'However, if the pressure of the film forming chamber is higher than 200 Pa, the pressure in the gas mixing space will significantly increase in proportion to the pressure of the film forming chamber. When the film is formed to a pressure of 200 Pa, the piping is easily blocked. (Embodiment 3) The conceptual diagram of FIG. 7 shows a film forming apparatus of Embodiment 3. Compared with the film-forming apparatus of FIG. 5, the film-forming apparatus of FIG. 7 is different only in that the exhaust port 5 and the exhaust pipe 6 are arranged below the center of the heater 2. The exhaust port 5 is arranged below the center of the heater 2, so that the airflow discharged from the film forming chamber 3 can approach the center of the substrate 1 symmetrically. It should be noted that, in Examples 3 and later, a spray vaporizer is used. (Embodiment 4) 99619.doc -28- 200535275 The schematic plan view of FIG. 8 is based on Embodiment 4, and the thickness distribution when the zinc oxide film is formed on the glass substrate 1 of FIG. Here: Addition Example 4 t ′ When forming the oxide film, the gas migration force and the gas flow rate are the same as those in Example 2. In the figure, the value of the emperor τ represents the height of the film thickness in the early position. Comparing FIG. 8 with FIG. 6, it can be seen that, in the fourth embodiment, “mesh ratio” with the embodiment can be pushed by 10K ¥ π +. _ J to improve the uniformity of M thickness. In FIG. 8 The size of the thinner areas of the four corners of the substrate is roughly the left and right sides of the substrate

the same. Compared with the thickness of the central region of the substrate, more than 75% of the film thickness region 'is 99.0% of the substrate area, and more than 95% of the film thickness region is 96.9% of 9690 cm2 of the substrate area. (Embodiment 5) The longitudinal sectional view of the concept of Fig. 9A shows the film forming apparatus of Embodiment 5, and the plan view of the concept of Fig. 9B shows the exhaust port arrangement in the film forming apparatus of Fig. 9A. As shown in FIG. 9A, an exhaust pipe is arranged below the center of the heater 2. 9A and 9B, it can be understood that shielding plates 14 for blocking airflow are arranged along the four sides of the lower surface of the heater 2. An exhaust port 51 is provided at each center of the four shield plates 14 along the four sides of the heater 2. The reaction gas supplied to the glass substrate 1 from the hole of the shower plate 10 forms a transparent conductive film on the heated substrate 丨, and then flows approximately symmetrically to the periphery of the substrate 1 and is discharged through the four exhaust ports 5 丨. gas. Further, there may be a slight gap between the corners between the shield plate 14 and the heater 2 and the corners where the shield plates are in contact with each other. (Embodiment 6) The schematic plan view of Fig. 10 is taken as Embodiment 6, and the thickness distribution when the oxide film is formed on the glass substrate 1 of 1 mxl m with the film forming apparatus of Fig. 9a. In this sixth embodiment of 99619.doc -29-200535275, when the zinc oxide film is formed, the gas pressure and gas flow rate are the same as those in the second embodiment. The values in Fig. 10 are contour lines of the film thickness in units. Comparing Fig. 10 with Figs. 6 and 8, it can be seen that, compared with Examples 2 and 4, in this Example 6, the film thickness uniformity can be further improved. In FIG. 10, the sizes of the thinner film thickness areas at the four corners of the substrate are approximately the same on the left and right sides of the substrate. Compared with the film thickness of the central area of the substrate, a film thickness area of 75% or more is 1,000% of the substrate area and 1,000 cm2, and a film thickness area of 95% or more is 994% of the substrate area. cm2. (Embodiment 7) The longitudinal sectional view of the concept of Fig. 11A shows the film forming apparatus of Embodiment 7, and the plan view of the concept of Fig. 11B shows the exhaust port arrangement in the film forming apparatus of Fig. UA. In this case, the gas in the film forming chamber 3 is sucked in through the plurality of exhaust ports 52 provided in the branch exhaust pipe 15, and is exhausted through the branch exhaust pipe 15 and the exhaust pipe 6. Most of these exhaust ports 52 are arranged approximately symmetrically near the opposite sides of the glass substrate i, whereby the exhaust of the gas can be performed approximately symmetrically in the center of the substrate surface. 7 and 9A, the exhaust pipe 6 is arranged below the center of the heater 2. However, in the seventh embodiment, the exhaust pipe 6 may be arranged on the side of the vacuum tank 4. Therefore, when there are some restrictions on the arrangement of the exhaust pipe 6 under the vacuum tank 4, the seventh embodiment is preferred. In addition, in the case of forming a film by arranging a plurality of substrates in parallel in a horizontal direction, in order to maintain the uniformity of the air flow on each substrate surface, it is preferable to provide an exhaust port along the opposite side of the substrate, and the exhaust pipe 6 is also As shown in FIG. 11A, it is preferable to arrange on the side surface of the vacuum tank 4. (Embodiment 8) 99619.doc -30- 200535275 The schematic plan view of Fig. 12 is taken as embodiment 8, and the thickness distribution when a zinc oxide film was formed on a glass substrate of 1 mxl m with the film-forming device of "A" was formed. In the eighth embodiment, the gas pressure and the gas flow rate when forming the zinc oxide film are the same as those in the second embodiment. The values in Figure 12 represent the film-thickness contours in handsome units. When FIG. 12 is compared with FIG. 6, FIG. 8, and FIG. 10, the film thickness uniformity can be further improved in this example 8 as compared with the examples 2, 4, and 6. In FIG. 12, the sizes of the thinner and thicker areas at the four corners of the substrate are approximately the same on the left and right sides of the substrate. Compared with the film thickness in the center area of the substrate, 75% or more of the film thickness area is 100% of the substrate area. / 〇 of 10000 cm2, with a film thickness area of more than 95% is 99 7% of 997.0 cy of the substrate area. (Embodiment 9) The longitudinal sectional view of the concept of Fig. 13A shows the film-forming apparatus of Embodiment 9, and the plan view of the concept of Fig. 13B shows the exhaust port arrangement in the film-forming apparatus of Fig. 13A. As shown in FIG. 13A, an exhaust pipe 6 is arranged below the center of the heater 2. 13A and 13B, shield plates 14 for blocking airflow are arranged along four sides of the lower surface of the heater 2. As shown in FIG. Exhaust ports 53 are provided under the corners of the heater 2. The reaction gas supplied to the glass substrate from the hole of the shower plate 10 forms a transparent conductive film on the heated substrate 1, and thereafter, the air flows approximately symmetrically to the four corners of the substrate 1, and is exhausted by the four exhaust ports 53. gas. Further, the corner portion between the shield plate 14 and the heater 2 may have a slight gap. (Embodiment 10) The schematic plan view of Fig. 14 is taken as Embodiment 10, and the thickness distribution when a zinc oxide film was formed on a 1 mxl m glass substrate using the film forming apparatus of Fig. 13A. 99619.doc 31 200535275 In Example 10, when the oxide film was formed, the gas pressure and gas flow were the same. The numerical values in Fig. 14 are the isometric lines of the film thickness in units of ㈣. Comparing FIG. 14 with FIG. 6, FIG. 8, FIG. 10, and FIG. ^, It can be seen that compared with Examples 2, 4, 6, and 8, in this Example 10, y is further improved: film thickness is further improved Uniformity. In Fig. 14, the film thickness at the four corners of the substrate is almost non-existent. Compared with the thickness of the central area of the substrate, more than 75% of the film thickness area is 1000% of the substrate area, and 100% of the substrate area is 100% of the substrate area. 〇〇〇cm2. (Embodiment 11) The σ 彳 plane view of the S mode shows the photoelectric conversion device of Embodiment 11. This photoelectric conversion device includes, as a surface transparent electrode 17, a zinc oxide film 'formed on a glass substrate 16 using the film forming device of Fig. 5. On the surface electrode π, a first thin-film photoelectric conversion unit 18 including a pin semiconductor junction and a second thin-film photoelectric conversion unit 19 including a pin semiconductor junction are formed by an electric tCVD method, and a back metal is formed thereon by an epitaxial method. Electrode 2 〇. In this photoelectric conversion device, light incident from the glass substrate 16 side is subjected to photoelectric conversion by the first photoelectric conversion unit 8 and the second photoelectric conversion unit 9 having a hybrid structure. The first photoelectric conversion unit 18 is composed of a first type semiconductor layer 18a of amorphous silicon carbide doped with B, a first true semiconductor layer of amorphous silicon 丨 8b, and a first n type of microcrystalline silicon doped with P. The semiconductor layer 18c is configured. The second photoelectric conversion unit 19 is composed of a second p-type semiconductor layer 19a doped with microcrystalline silicon doped with B, a second true semiconductor layer 19b with polycrystalline silicon, and a second n-type doped with microcrystalline silicon. The semiconductor layer 19c is configured. Compared with amorphous silicon, polycrystalline silicon can absorb 99619.doc -32- 200535275. Fortunately, long-wavelength light is not completely absorbed by the first true semiconductor layer 18b, so it can be absorbed by the second true semiconductor layer 19b. Absorption, which can improve the maximum power (pmax) of the photoelectric conversion device. The photoelectric conversion device of this embodiment 11 is formed using a glass substrate having an area of 91 cm × 45.5 cm, and a semiconductor stacked structure on the substrate is patterned by laser to form a integrated photoelectric conversion module as shown in FIG. 19 Of the structure. At this time, 100 segments of the photoelectric conversion cells 11 are electrically connected in series. As a result, in the characteristics of the large-area photoelectric conversion device of Example 1 丨, the maximum power (Pmax) was 38.7 w, the open voltage (Voc) was 131.9 V, the short-circuit current (Isc) was 0.432 A, and the curve The factor (FF) is 0.679. (Comparative Example 6) As Comparative Example 6, a photoelectric conversion device including a transparent conductive film formed using the film forming apparatus of Fig. 3 as a surface electrode was produced. Compared with Example u, the difference lies in the method of forming only the transparent conductive film in the photoelectric conversion device of Comparative Example 6. As a result, among the characteristics of the large-area photoelectric conversion device of Comparative Example 6, Pmax = 3.6 w, voc = 84 5 V, Isc = 〇3〇4 A, and FF = 0.40. That is, the characteristics of the photoelectric conversion device of Comparative Example 6 are very low; relatively, it can be seen that the photoelectric conversion device of Example 丨 can significantly improve its characteristics. ', (Embodiment 12) A cross-sectional view in the mode of Fig. 16 shows a photoelectric conversion device according to Embodiment 12. The photoelectric conversion device of the twelfth embodiment differs from the embodiment of FIG. 15 only in that a zinc oxide film formed by the film-forming device of FIG. 3 is inserted between the second n-type semiconductor layer 19c and the back electrode 20. The rear surface reflection layer 21. By setting this 99619.doc »33- 200535275 back reflective layer 21, the light reflectance of the back can be increased. Therefore, long-wavelength light that is not completely absorbed by the first true semiconductor layer 18b or the second true semiconductor layer 19b can be reflected at the interface between the second n-type semiconductor layer 19c and the back reflective layer 21 and used for photoelectric conversion. Can improve the characteristics of the photoelectric conversion device. Moreover, in Example 12, the thickness of the back reflection layer 21 was 80 nm. In the characteristics of the large-area photoelectric conversion device of Example 12, Pmax = 41.5 W, Voc = 132.5 V, Isc = 0.452 A, and FF = 0.693. Its characteristics are also higher than those of Example 11. (Embodiment 13) A cross-sectional view in the mode of FIG. 17 shows a photoelectric conversion device according to Embodiment 13. The photoelectric conversion device of the thirteenth embodiment is different from the twelfth embodiment of FIG. 16 only in that the oxidation formed by the film forming device of FIG. 5 is inserted between the first n-type semiconductor layer i8c and the second p-type semiconductor layer i9a Middle layer 22 of zinc film. By providing this intermediate layer 22, light that is not completely absorbed by the first true semiconductor layer 1 讣 can be reflected at the interface between the first n-type semiconductor layer i8c and the intermediate layer 22 and be reflected in the first true semiconductor layer 18b. Used for photoelectric conversion. In addition, since the light passing through the intermediate layer 22 can be scattered by the uneven structure on the surface of the intermediate layer 22, the substantial optical path length in the first true semiconductor layer 19b can be extended. Therefore, in the photoelectric conversion device of Example 13, the utilization efficiency of light is improved by the intermediate layer 22, and the photoelectric conversion characteristics can be further improved. In Embodiment 13, the thickness of the intermediate layer 22 is 50 nm. In the characteristics of the large-area photoelectric conversion device of Example 13, Pmax = 43.3 W, Voc = 133.8 V, Isc = 0.463 A, and FF = 0.699. Its characteristics are also higher than those of Example 12. (Example 14) 99619.doc -34- 200535275 Figure? The cross-sectional view of the mode shows the photoelectric conversion device of the embodiment ". The difference between the photoelectric conversion device and the embodiment 11 of Fig. 15 is that the silicon oxide η 1 is dispersedly applied between the glass substrate 16 and the surface electrode 17.成 的 底 底 23. The surface of the transmissive electrical film is concave on the surface of the electrode 1 ~ T T can scatter light and extend the substantial optical path of the photoelectric conversion device. When the thickness of the transparent conductive film is large, it is transparent and conductive. The light absorption deduction is also increased. Therefore, a bottom layer with a large surface unevenness is formed using oxygen-cut particles that are substantially transparent to light of a wavelength available to the photoelectric conversion device. On the bottom layer 23, a transparent conductive film is formed using the film-forming device of FIG. When the surface electrode 17 is used, the surface can suppress the absorption loss of the surface electrode 17 and increase the surface unevenness. The bottom layer 23 can be formed by coating the glass substrate with calcareous particles dispersed in a gel-like solvent on the glass substrate. The characteristics of the large-area photovoltaic and wheat-changing device of this embodiment M are: pmax = 41.9 w, 3 v, Isc-0.461 A, and FF = 0.687. Its characteristics are higher than those of the embodiment. (Implementation Example 15) In Example 15, and Example丨 The transparent conductive film is also formed using the film-forming device of FIG. 5. However, the difference lies only in the embodiment. The piping distances A and B used are both 0.15 m. In this regard, in Example 15 The distance A and B are both extended to 1 m. In Example 1, even if the film formation time is 300 hours in total, the piping will not be blocked. However, when the total time is about 400 hours, the flow rate of the DEZ vapor will change. If it is unstable, the powder adheres to the DEZ supply valve 24 and is blocked. On the other hand, in Example 15, even if the film formation is performed for a total of 700 hours or more, the piping will not be blocked. At this time, the DEZ supply valve 24 and Ηβ None of the supply valves 25 was 99619.doc -35- 200535275 occlusion caused by raw powder. (Example 16) In Example 16 as well, in the same manner as in Example 丨, the film-forming device of FIG. 5 was used to form translucent conductivity. However, in Example i 6, an additional twelve piping which is combined with the gas and two ports 12 was added, and an additional mixed reaction gas of B2H6 and η was prepared. When the zinc oxide film was formed, the pressure in the vacuum tank 4 10 Pa, substrate temperature 150 ..., DEZ vapor flow rate is 300 sccm h2〇 vapor inside his ilk to 1000 seem, B2H62 flow i 5 sccm, flow rate of H2 is 5〇〇

The flow rates of seem and Ar are the total of 500 seem for the DEZ supply pipe 7 and the H20 supply pipe 8. In the sixteenth embodiment, the sheet resistance of the transparent conductive film can be reduced by the supply of the bazaar. In addition, by supplying H2, the uniformity of the substrate temperature can be maintained under a low film forming pressure, not only the thickness uniformity of the transparent conductive film, but also the uniformity of light transmittance and sheet resistance. (Embodiment 17) The longitudinal sectional view of the concept of Fig. 26A shows the film-forming apparatus of Embodiment 17, and the longitudinal sectional view of the concept of Fig. 26B shows the arrangement of exhaust ports in the film-forming apparatus of Fig. 26A. The film-forming device of this embodiment 17 is similar to the film-forming device of embodiment 9 shown in FIGS. 13A and 13β, but the film-forming device of embodiment 9 is a horizontal type. In contrast, the film-forming device of embodiment 17 It is vertical. In addition, the film forming apparatus of FIG. 26A has two shower plates 10 in parallel. Therefore, when a plurality of substrates are arranged facing the two shower plates 10, the film can be efficiently formed. In order to spray the reaction gas uniformly from the shower plates 10 on both sides, the reaction gas pipe 11 is extended to the vicinity of the center of the shower plate 10, and the reaction gas is supplied to the shower plate from there. The surface of the shower plate 10 is controlled by temperature, so it extends to the reaction gas piping inside the shower 99619.doc -36- 200535275. Even if a wall heater 13 is attached, the reaction gas piping can be maintained there.丨 roughly the same temperature. In the vertical film-forming device, the main surface of the substrate 丨 is arranged in the vertical direction, so even if dust is peeled off from the deposits attached to the inner wall of the film-forming chamber, the shower plate 丨 0, and the heater 2, the dust is not It will fall and adhere to the main surface of the substrate, so that pinhole-like pinholes can be prevented from occurring on the transparent conductive film formed on the substrate. Therefore, the vertical film-forming device can be longer than the horizontal film-forming device. There is no need to yoke the cleaning in the film forming chamber, and the film formation can be continued stably.

In addition, in the film-forming apparatus of this embodiment 17, two spraying plates 面对 can be arranged to face two substrates with an area of 0.5 mxl m (see FIG. 26B). In this case, four substrates i can be simultaneously installed. Film formation. The transparent conductive film formed by the film forming apparatus of this embodiment has a uniform film thickness distribution similar to that of Example 9. (Embodiment 18) The longitudinal sectional view of the concept of Fig. 27A shows the film-forming apparatus of Embodiment 18, and the longitudinal sectional view of the concept of Fig. 27B shows the exhaust port arrangement in the film-forming apparatus of Fig. 27A. When the vertical film-forming apparatus of this embodiment 18 is in accordance with the drawings "A, 11B, and 26A, it can be understood that the features including one part of the embodiment 7 and the features of the -part of the embodiment are included. According to this implementation, the film-forming device 'can face 4 spraying plates 10 and be configured. _ Block of hungry area 'can be formed on 4 large-area substrates at the same time. The transparent conductive film formed by the film forming apparatus of this embodiment has a uniform film thickness distribution as in Example 7. '' In the use of organometallic vapor and oxidant [Industrial availability] As described above, according to the present invention, the low-pressure thermal CVD of 99619.doc -37- 200535275 vapor can form a large transparent conductive film . —As a result, it is possible to provide a large-area photoelectric conversion device containing a transparent conductive film and a large area with improved characteristics. [Simple illustration] Figure 1 is a conceptual diagram showing a conventional example of forming a transparent conductive film. Figure 2 is a thickness analysis of the transparent conductive film formed by the film forming apparatus of Figure 1 Figure 0

Fig. 3 is a conceptual diagram showing another example of a conventional film-forming apparatus for forming a transparent electric film. FIG. 4 is an eight diagram of the thickness of the transparent conductive film formed by the film forming apparatus of FIG. 3. FIG. FIG. 5 is a conceptual diagram of a film forming apparatus according to an embodiment of the present invention. FIG. 6 is a thickness map of the transparent conductive film formed by the film forming apparatus of FIG. 5. FIG. 7 is a conceptual diagram of a film forming apparatus according to another embodiment of the present invention. Fig. 8 is a thickness distribution of a transparent conductive film formed by the film forming apparatus of Fig. 7; Fig. 9A is a longitudinal sectional view showing the concept of a film forming apparatus according to another embodiment of the present invention. Fig. 9B is a plan view showing the concept of the arrangement of exhaust ports in the film forming apparatus of Fig. 9A. Fig. 10 is a thickness distribution of a transparent conductive film formed by the film forming apparatus of Fig. 9A. Fig. 0 99619.doc -38- 200535275 Fig. 11A is a longitudinal sectional view showing the concept of a film forming apparatus according to another embodiment of the present invention. Fig. 11B is a plan view showing the concept of the arrangement of exhaust ports in the film forming apparatus of Fig. NA. Fig. 12 is a thickness distribution diagram of a transparent conductive film formed by the film forming apparatus of Fig. 11A. Fig. 13A is a longitudinal sectional view showing the concept of a film forming apparatus according to still another embodiment of the present invention. Fig. 13B is a plan view showing the concept of the arrangement of exhaust ports in the film forming apparatus of Fig. 13A. Fig. 14 is a thickness distribution diagram of a transparent conductive film formed by the film forming apparatus of Fig. 13A. Fig. 15 is a sectional view showing a mode of a photoelectric conversion device according to still another embodiment of the present invention. Fig. 16 is a sectional view showing a mode of a photoelectric conversion device according to still another embodiment of the present invention. Fig. 17 is a sectional view showing a mode of a photoelectric conversion device according to still another embodiment of the present invention. Fig. 18 is a sectional view showing a mode of a photoelectric conversion device according to still another embodiment of the present invention. Fig. 19 is a sectional view showing a mode of a large-area photoelectric conversion device according to still another embodiment of the present invention. FIG. 20 is a conceptual diagram showing another example of a conventional film forming apparatus. Fig. 21 is a schematic diagram showing the distribution of 99619.doc -39- 200535275 tubes near the gas mixing space of the film forming apparatus of the present invention. Fig. 22 is a graph showing the relative density of H20 existing in the DEZ supply pipe depending on the distance from the gas mixing space. Figure 23 is a conceptual diagram of an evaporative gasifier. Figure 24 is a conceptual diagram of a bubble gasifier. Figures 25 (a)-(b) are conceptual diagrams of a spray gasifier. Fig. 26A is a longitudinal sectional view showing the concept of a film forming apparatus according to still another embodiment of the present invention. p Fig. 26B is a longitudinal sectional view showing the concept of the arrangement of exhaust ports in the film forming apparatus of Fig. 26A. Fig. 27A is a longitudinal sectional view showing the concept of a film forming apparatus according to still another embodiment of the present invention. Fig. 27B is a longitudinal sectional view showing the concept of the arrangement of exhaust ports in the film forming apparatus of Fig. 27A. In the drawings of the present case, the same reference signs denote the same or corresponding parts. • [Description of main component symbols] 1 Glass substrate 2 Heater 3 Film forming chamber 4 Vacuum tanks 5, 51, 52, 53 Exhaust port 6 Exhaust pipe 7 DEZ supply pipe 99619.doc -40- 200535275 8 H20 supply pipe 9 Diffusion box 10 Shower plate 11 Reactive gas piping 12 Gas mixing space 13 Wall heater 14 Sheath plate 15 Branch exhaust pipe 16 Glass substrate 17 Surface electrode 18 First photoelectric conversion unit 18a First P-type semiconductor layer 18b First authenticity Semiconductor layer 18c First n-type semiconductor layer 19 Second photoelectric conversion unit 19a Second p-type semiconductor layer 19b Second true semiconductor layer 19c Second n-type semiconductor layer 20 Back electrode 21 Back reflective layer 22 Intermediate layer 23 Bottom layer 24 DEZ supply Valve 25 Η 20 Supply valve 99619.doc -41-200535275

26 Heater 27 Tank 28 Liquid material 29 Vapor 30 Gas mass flow controller 31 Gravimeter 32 Thermostatic bath 33 Bubble 34 Gas mass flow controller 35 Liquid mass flow controller 36 Mixer 37 Ar supply pipe 38 Liquid material supply pipe 39 Micro Hole 40 Mist liquid material 41 Vaporized gas supply tube 71 Heater 81 Heater 101 Integrated thin-film photoelectric conversion module 102 Glass substrate 103 Surface electrode layer 104a First photoelectric conversion unit 104b Second photoelectric conversion unit 106 Back electrode layer 99619 .doc -42- 200535275 110 photoelectric conversion cell 121 first separation groove 122 second separation groove 123 connection groove 99619.doc

Claims (1)

200535275 The scope of the patent application: 1. A film-forming device, which is characterized by: a film-forming chamber for depositing a transparent conductive film on a bottom layer having an area of more than 22 cm2 by CVD; and conveying a gas containing organic metal vapor The first gas pipe; the second gas pipe that conveys the second gas containing oxidant vapor; the first and second gas pipes are combined to mix the gas mixing space for the first and second gas; A gas introduction means for introducing the mixed reaction gas into the front membrane chamber in the gas mixing space; and an exhaust device for exhausting the exhaust gas from the film forming chamber. 2. The film-forming device as described in item 1 above, wherein the gas introduction means is composed of a number of gas emission elements, such as +, from α, and r, which can control the above-mentioned reaction gas to between 20 and 100. Temperature within the range. 3. For example, if the above-mentioned cross-sectional area of item 1 is required, "The gas mixing space has a 99619.doc 200535275 holding means or a heater. Δ ·: The film-forming device of the requester 'which Contains a base for holding the aforementioned bottom layer: a holding means or a heater for holding the aforementioned bottom layer, the exhaust device is connected to an exhaust port facing the aforementioned base holding means or the aforementioned heating device. 9 · If requested The setting of 2 is a method in which the center of the aforementioned shower plate is provided with a plurality of exhaust ports symmetrically in the aforementioned film forming chamber. 10. A film forming method, the fourth characteristic of which is that it uses CVD to make transparent Conductive • The film is deposited on the bottom layer arranged in the forming chamber; and before the second gas containing organic metal vapor and the second gas containing oxidant vapor are introduced into the aforementioned film forming chamber, they are mixed into a reaction in the gas mixing space. Gases. 11. The film-forming method according to claim 10, wherein the aforementioned transparent conductive film is oxidized. 12. The film-forming method according to claim H), wherein the aforementioned organometallic vapors are based on sintered radicals. • 13 .Such as Method for film formation of term 10, wherein said oxidant vapor system contains selected from water, oxygen, carbon dioxide, carbon monoxide, dinitrogen oxide, nitrogen dioxide, sulfur dioxide, dinitrogen pentoxide, alcohols (R (〇H)), Ketones (R (CO) R '), ethers (ROR,), aldehydes (R (co)), amidoamines ((RCO) x (NH3-x), χ =: ι, 2, 3) and at least one of the sub-stone breeze (R (s〇) R,) (wherein r and RW are calcined groups.) 14. The film-forming method according to claim 10, wherein the film is conveyed to the aforementioned gas mixing space. At least one of the aforementioned organometallic vapor and the aforementioned oxidant vapor is a mixture with a carrier gas of 99619.doc 200535275. 15. The method of Gan Qiyi and Zhishi M ^ Fengyao as claimed in claim 14, wherein the organometallic vapor and the aforementioned oxidant At least-the side of radon gas is gasified by the foaming method. # 月 长 ^ 14The film formation method, where at least-the aforementioned organometal vapor and the emulsifier sacrificial gas are gasified by the spray gasifier 17. In accordance with the method of claim 1 (), the airflow path from the aforementioned gas mixing space to the aforementioned agent to within Those controlled at a temperature in the range of 20 to 10 ° C. 18. The film forming method as claimed in item 10, wherein the aforementioned reaction gas system is introduced into the aforementioned film forming chamber through a shower plate containing most gas release holes. 19. If the film-forming method of item 18 is requested, wherein the aforementioned shower plate can control the aforementioned reaction gas to a temperature in the range of 20 to 10 (rc). 2 0 · Such as 6 extravagant film-forming of 1 〇 Fang, Mugan a 乂 membrane method, in which the pressure in the gas mixing space is adjusted to less than 13,000pa. 21. A photoelectric conversion device ', characterized in that a transparent conductive film is formed on a surface electrode by the film-forming method of claim 10. 22 ·-A type of photoelectric transformer, characterized in that it is a transparent conductive film formed on the back electrode by the film-forming method of claim 10. 23. A photoelectric conversion device ', characterized in that it comprises a transparent conductive film formed by a film forming method according to claim w. ^ 卞 Guarding the middle layer of the armguards 99619.doc