AMORPHOUS SEMICONDUCTOR AND AMORPHOUS SILICON PHOTOVOLTAIC DEVICE

Abstract: An amorphous silicon semiconductor of the general formula: a-Si (l-x-y) C x N y containing hydrogen and/or fluorine, which provides an amorphous silicon PIN junction photovoltaic device having an improved conversion efficien­ cy when it is used as a P-type or N-type semiconductor (10) in the layer on the light impinging side of the PIN junction photovoltaic device. Also, the conversion efficiency of an amorphous silicon PIN junction photovoltaic device is im­ proved by using a film of ITO and SnO₂ two layer structure as a transparent electrode (11) for the photovoltaic device with the SnO₂ layer contacting the P or N layer (10), and the improvement is particularly marked in the heterojunction photovoltaic device.

Description: The present invention relates to an amorphous silicon semiconductor and an amorphous silicon photovoltaic device. Since it was found in 1976 by W.E. Spear et al that the conductivity of the amorphous silicon obtained by a plasma decomposition method of silane (SiH₄) could be greatly altered by doping with phosphine (PH₃) and diborane (B₂H₆) and an amorphous silicon solar cell was fabricated on an experimental basis in 1976 by D. E. Carlson et al, the amorphous silicon solar cell has attracted attention and a study of improvement of its efficiency has been lively made. The Schottky barrier type, PIN type, MIS type and heterojunction type are known as structures of photovoltaic devices using an amorphous silicon thin film. The former three types promise to provide high efficient solar cells. For instance, a Schottky barrier type solar cell made by D. E. Carlson et al in 1977 showed a conversion efficiency of 5.5%, a MIS type solar cell made by J. I. B. Willson et al in 1978 showed a conversion efficiency of 4.8%, and a PIN junction solar cell made by Yoshihiro Hamakawa in 1978 showed a conversion efficiency of 4.5%. In case of the PIN junction solar cell, the P or N type amorphous silicon gives a short carrier life time and, therefore, fails to provide an effective cell. Also, the P-layer suffers from heavy absorption loss of light because it has a higher light absorption coefficient than the I-layer. In order to eliminate these drawbacks, an inverted PIN junction photovoltaic device has been proposed. This photovoltaic device is constructed so that the light impinges on the N-type amorphous silicon side. Since this device has a smaller light absorption coefficient than the P-type, it is believed to be more advantageous, though slightly. Nevertheless this N-type amorphous silicon is no better than the P-type in the sense that it similarly suffers from absorption loss of light. Amorphous silicon containing 5.10¹⁹cm⁻³ of carbon and 7.10¹⁸cm⁻³ of nitrogen used in a p-i-n solar cell is described in Extended Abstracts vol. 80-2 October 1970, Abstract No. 572, pages 1428-1429. Also, in case of the PIN junction solar cell, it is necessary to attach a transparent electrode onto the light-impinging side, and ITO (indium-tin-oxide) (In₂O₃+SnO₂) or SnO₂ has been employed as a transparent electrode. However, the ITO electrode has the disadvantage that the curve fill factor is good, but the open circuit voltage is low, and the SnO₂ electrode has the disadvantage that the open circuit voltage is high, but the curve fill factor is bad. It is an object of the present invention to provide an amorphous silicon semiconductor suitable for use in fabricating an amorphous silicon PIN junction photovoltaic device. Another object of the invention is to provide an amorphous silicon PIN junction photovoltaic device having an improved conversion efficiency. These and other objects of the present invention will become apparent from the description hereinafter. It has now been found that the short-circuit current density and the open circuit voltage are greatly improved by using in at least one of the P and N layers of PIN junction photovoltaic device a P-type or N-type doped thin film of a hydrogenated amorphous silicon carbon nitride of the general formula: a-Si (1-x-y) C x N y :H or a partially fluorinated amorphous silicon carbon nitride of the general formula: a-Si (1-x-y) C x N y :F:H (they being hereinafter referred merely to as "amorphous silicon carbon nitride" or "a-Si (1-x-y) C x N y "). In accordance with the present invention, there is provided an amorphous silicon carbon nitride semiconductor according to claim 1. The present invention also provides an amorphous silicon PIN junction photovoltaic device according to claim 2. The photovoltaic device of the present invention is useful as solar cells, photoswitches, and the like. Fig. 1(a) is a schematic view illustrating the structure of a photovoltaic device of the type wherein the light impinges on the P-layer side; Fig. 1(b) is a schematic view illustrating the structure of a photovoltaic device of the type wherein the light impinges on the N-layer side; Fig. 2 is a diagram showing an energy band profile of the PIN heterojunction photovoltaic device of the present invention; Fig. 3 is a graph showing the relationship between the diffusion potential (Vd) and the open circuit voltage (Voc) as obtained with the P-type amorphous semiconductor on the window side; Fig. 4(a) is a schematic view illustrating the structure of a photovoltaic device of another type according to the present invention that the light impinges on the P-layer side; and Fig. 4(b) is a schematic view illustrating the structure of a photovoltaic device of another type according to the present invention that the light impinges on the N-layer side. The term "amorphous silicon" as used herein means the hydrogenated ones or fluorinated ones, and comprehends amorphous silicon derivatives such as a-SiGe:H, a-SiGe:F:H, a-SiSn:H, a-SiSn:F:H, a-SiSnGe:H, a-SiSnGe:F:H and so on. Amorphous silicon used in the present invention is obtained by subjecting a mixed gas containing a silicon compound, e.g. monosilane, a polysilane such as disilane, silane fluoride or a derivative thereof, or a mixture thereof, and hydrogen or an inert gas such as argon or helium diluted with hydrogen, and if necessary, further with GeH₄ and/or SnH₄, to radio-frequency glow decomposition or DC glow discharge decomposition by the capacitive or inductive coupling method. The concentration of silane in the mixed gas generally is in the range of from 0.5 to 100%. The concentration of the silane derivatives is suitably determined in accordance with the composition of the desired product and the glow discharge decomposition condition. A substrate is desired to have a working temperature in the range of from about 200 to about 300°C. The substrates used in the invention include a glass sheet having a transparent electrode (e.g. ITO and SnO₂) vacuum deposited thereon, a metallized polymer film, a metal sheet and all other known materials used as substrates in the fabrication of a solar cell. Typical examples of the basic construction of a solar cell are shown in Figs. 1(a) and 1(b). Illustrated in Fig. 1(a) is a solar cell of the type that the light impinges on the P-layer side. For instance, the solar cell of this type has a construction of glass-transparent electrode -P-I-N-AI. Illustrated in Fig. 1(b) is a solar cell of the type that the light impinges on the N-layer side. For instance, the solar cell of this type has a construction of stainless steel -P-I-N-transparent electrode. Optionally, other constructions may be formed by interposing a thin insulation layer or a thin metal layer between the P-layer or N-layer and the transparent electrode. Any construction suffices so far as the PIN junction is included as the basic component. Intrinsic amorphous silicon (hereinafter referred to as "I-type a-Si") obtained by the glow discharge decomposition of silane or a derivative thereof, silane fluoride or a derivative thereof, or a mixture thereof, and an amorphous silicon derivative such as a-SiGe or a-SiSn, which have a carrier life time of not less than about 10⁻⁸ second, a density of localized state not more than about 10¹⁸cm³eV¹ and a mobility of not less than 10⁻⁴cm²/V · sec, are employed in the present invention as an I-layer of amorphous silicon derivative photovoltaic cells. The I-type a-Si and the amorphous silicon derivative may be employed alone or in combination thereof as an I-layer. The PIN junction structure is formed by joining P-type and N-type doped amorphous silicon semiconductors to the I-layer. The construction contemplated by the present invention is characterized by using, in at least one of the P-layer and N-layer, specifically in the layer on which the light impinges, a P or N type amorphous semiconductor of the general formula: a-Si (1-x-y) C x N y , containing hydrogen or fluorine. Both of the P and N layers may be made of this particular amorphous semiconductor. The doped layer which does not use the above-mentioned particular amorphous semi-conductor of the present invention is formed by doping the above-mentioned I-type a-Si with an element of Group III of the Periodic Table to provide the P-type a-Si, or by doping with an element of Group V of the Periodic Table to provide the N-type a-Si. This P-type or N-type a-Si may be used in combination with or replaced with the P-type or N-type amorphous silicon derivatives. The amorphous semiconductor of the present invention is made of amorphous silicon carbon nitride represented by the general formula: a-Si (1-x-y) C x N y . The amorphous silicon semiconductor of the general formula: a-Si (1-x-y) C x N y in which x and y satisfy the following equations: 0.05≦x≦0.75, 0.05≦y≦0.75 and 0.1≦x+y≦0.80, is preferable. The amorphous silicon carbon nitride is obtained by subjecting the above-mentioned silicon compound, e.g. silicon hydrides such as SiH₄ or silicon fluorides such as SiF₄, a carbon compound such as hydrocarbons or carbon fluoride, and a nitrogen compound, e.g. nitrogen or hydrogenated nitrogens such as NH₃ and hydrazine, to the glow discharge decomposition. It contains 0.5 to 30 atom % of hydrogen and/or fluorine. When the amorphous silicon carbon nitride semiconductor is employed as a P-layer or N-layer of a photovoltaic device, it is doped with P-type or N-type impurities. The P-type or N-type amorphous semiconductor having an optical band gap of not less than about 1.85 eV, an electric conductivity not less than about 10⁻⁸(Ω. cm)⁻¹ at 20°C and a diffusion potential (Vd) (exhibited in the PIN junction) of not less than about 1.1 volts is preferred. The amorphous silicon carbon nitride semiconductor of the present invention has a large optical band gap and exhibits a very high open circuit voltage (Voc), though the semiconductor, when used as a window material for the PIN junction photovoltaic device, naturally has a possibility of increasing the shortcircuit current density (Jsc). It has been found that in the photovoltaic device of the present invention, there is the correlation between the diffusion potential (Vd) and the open circuit voltage of the device as depicted by the band profile of Fig. 2. Although the diffusion potential (Vd) in the case of the invention exceeds about 1.1 volts, the trend of the relation is nearly constant without reference to the kind of the amorphous semiconductor to be used on the side exposed to the incident light. This diffusion potential is the difference obtained by subtracting the fermi level (Ef) of the P, N doped layers from the optical band gap (Eg.opt) of the amorphous semiconductor on the side exposed to the light. Let Ecn stand for the energy level of the conduction band on the N side and Evp for the energy level of the valence band on the P side, and the activation energies ΔEp and ΔEn can be determined based on the dependency of electric conductivity on temperature as shown in Fig. 2. Since ΔEp=Ef-Evp holds for the P type and ΔEn=Ecn-Ef for the N type, there ensues eVd=Eg.opt-(ΔEp+ΔEn). In the case of the incidence of light which occurs on the N side, the diffusion potential is similarly obtained by subtracting the fermi level (Ef) of the P, N layers from the optical band gap (Eg.opt) of the N type amorphous semiconductor. It is preferable that the amorphous semiconductor of the invention shown by the general formula: a-Si (1-x-y) C x N y , has an optical band gap (Eg.opt) of at least about 1.85 eV and a diffusion potential (Vd) of at least about 1.1 volts. By employing the amorphous semiconductor which satisfies this requirement, the heterojunction photovoltaic device is allowed to enjoy a great improvement in short-circuit current density (Jsc) and open circuit voltage (Voc). It is further preferred that the electric conductivity of the amorphous semi-conductor of the invention is at least 10⁻⁸(Ω. cm)⁻¹ at room temperature. When the electric conductivity is less than 10⁻⁸(Ω. cm)⁻¹, the curve fill factor (FF) becomes small and the conversion efficiency of the obtained photovoltaic device is not practical. The PIN junction photovoltaic device provided by the present invention will be described specifically below. In one typical construction as shown in Fig. 1(a), this device is of the type that the light impinges on the P-layer side, and is composed of substrate 1 such as glass, transparent electrode 2, P-type amorphous semi-conductor 3, I-type amorphous silicon 4, N-type amorphous semiconductor 5 and electrode 6. The amorphous silicon carbon nitride semiconductor of the present invention is used at least in the layer on which the light impinges, and for instance, the photovoltaic cell of the invention has a construction of transparent electrode-P type a-Si (1-x-y) C x N y -I type a-Si-N type a-Si-electrode, with the transparent electrode side to be exposed to the incident light. The transparent electrode is desired to be formed of ITO or SnO₂, preferably the latter. The transparent electrode may be previously formed by vacuum deposition on a glass substrate or may be directly formed by vacuum deposition on the P type amorphous semiconductor. The P type a-Si (1-x-y) C x N y layer on the light impinging side is desired to have a thickness of from about 3 nm (30 Å) to about 30 nm (300 Å), preferably from 5 nm (50 Å) to 20 nm (200 Å). Although the thickness of the I type a-Si layer is not specifically limited in the device of the present invention, it is generally selected from about 250 nm (2,500 Å) to about 1,000 nm (10,000 Å). Also, the thickness of the N type a-Si layer is not specifically limited, but is usually selected from about 15 nm (150 Å) to about 60 nm (600 Å). Optionally, this N type a-Si layer may be substituted by the N type a-Si (1-x-y) C x N y of the present invention. In another typical construction as shown in Fig. 1(b), the device is composed of electrode substrate 7, P-type amorphous semiconductor 8, I-type amorphous silicon 9, N-type amorphous semiconductor 10 and transparent electrode 11, and the transparent electrode side is exposed to the light. The photovoltaic device of this type has a construction of transparent electrode-N type a-Si (1-x-y) C x N y -I type a-Si-P type a-Si-electrode. The N type a-Si (1-x-y) C x N y on the light impinging side is desired to have a thickness of from about 3 nm (30 Å) to about 30 nm (300 Å), preferably from 5 nm (50 Å) to 20 nm (200 Å). Although the thickness of the I type a-Si is not specifically limited, it is generally selected from about 250 nm (2,500 Å) to about 1,000 nm (10,000 Å). The thickness of the P type a-Si layer, which is not particularly limited, is generally selected from about 15 nm (150 Å) to about 60 nm (600 Å). Optionally, this P type a-Si layer may be substituted by the P type a-Si (1-x-y) C x N y of the present invention. The material for the transparent electrode and the method for the vacuum deposition thereof are the same as described above. The present inventors have also found that the curve fill factor and open circuit voltage can be greatly improved by providing ITO-SnO₂ layers as a transparent electrode on the light impinging layer of a PIN junction photovoltaic device so that the SnO₂ layer has a thickness of about 3 nm (30 Å) to about 50 nm (500 Å), preferably about 5 nm (50 Å) to 50 nm (500 Å), and comes into contact with the light impinging P or N layer. Accordingly, the present invention provides an amorphous silicon PIN junction photovoltaic device having a high conversion efficiency which is improved in that it has a structure of ITO-SnO₂-P-I-N or ITO-SnO₂-N-I-P and the thickness of the SnO₂ layer is from about 3 nm (30 Å) to about 50 nm (500 Å). Typical examples of the basic structure of the photovoltaic device according to the present invention are shown in Figs. 4(a) and 4(b). Illustrated in Fig. 4(a) is a photovoltaic device of the type that the light impinges on the P-layer side, and is composed of transparent substrate 21 such as glass, ITO film 23, SnO₂ film 23, P-type amorphous silicon 24, intrinsic amorphous silicon 25, N-type amorphous silicon 26 and electrode 27. For instance, the device of this type has a construction of glass-ITO-SnO₂-P-I-N-AI. Illustrated in Fig. 4(b) is a photovoltaic device of the type that the light impinges on the N-layer side, and is composed of ITO film 28, SnO₂ film 29, N-type amorphous silicon 30, intrinsic amorphous silicon 31, P-type amorphous silicon 32 and electrode 33 such as metal. For instance, the device of this type has a construction of stainless steel-P-I-N-SnO₂-ITO. Other constructions may be formed, for instance, by interposing a thin insulation layer or a thin metal layer between the P-layer or N-layer and the transparent electrode layer. Any constructions are adoptable so far as the transparent electrode of the ITO-SnO₂ two layer structure in which the SnO₂ layer has a thickness of about 3 nm (30 Å) and about 50 nm (500 Å), is provided on the P-layer or N-layer to be exposed to the light to form an ITO-SnO₂-P-I-N or ITO-SnO₂-N-I-P structure. The above-mentioned specific transparent electrode is applicable to the a-Si PIN homojunction and heterojunction photovoltaic devices. The ITO film in the present invention is formed by subjecting In₂O₃ containing 3 to 15% by weight of SnO₂ to an electron beam deposition or sputtering method. The SnO₂ film in the present invention is usually those doped with a slight amount of Sb, and is formed by an electron beam deposition, sputtering or chemical vapor deposition method. In case of providing on a transparent substrate 1 such as glass as shown in Fig. 4(a), ITO is deposited on the substrate and SnO₂ is then deposited thereon in a film having a thickness of about 3 to about 50 nm. Although the thickness of the ITO film is not particularly limited, it is usually selected from 60 nm (600 Å) to 400 nm (4,000 Å), especially from 60 nm (600 Å) to 200 nm (2,000 Å). In case of employing a metal electrode 23 as shown in Fig. 4(b), after forming amorphous silicon semiconductors 32, 31 and 30 on the metal electrode 23, the SnO₂ film 29 having a thickness of 3 to 50 nm and the ITO film are formed thereon in that order. Further improved results are obtained in fabricating a PIN heterojunction photovoltaic device by employing the transparent electrode of the ITO-SnO₂ two layer structure. In that case, an amorphous silicon semiconductor of the general formula: a-Si (1-x) C x or a-Si (1-y) N y , is employed in at least the layer which comes into contact with the SnO₂ layer, as well as the beforementioned a-Si (1-x-y) C x N y semiconductor of the present invention. The amorphous silicon carbide is formed by the glow discharge decomposition of a mixed gas containing a silicon compound and a carbon compound such as hydrocarbons, and the amorphous silicon nitride is formed by the glow discharge decomposition of a mixed gas containing a silicon compound and a nitrogen compound such as ammonia. They are doped with a P-type or N-type impurity such as phosphine or diborane. The present invention is more specifically described and explained by means of the following Example. Example Glow discharge decomposition was carried out at a radio-frequency of 13.56 MHz in a quartz tube having an inner diameter of 11 cm. An I-type a-Si was obtained by subjecting silane diluted with hydrogen to the glow discharge decomposition at 2 to 10 Torrs. A N-type a-Si was obtained similarly by subjecting silane diluted with hydrogen and phosphine (PH₃) (PH₃/SiH₄=0.5 mole %) to the glow discharge decomposition. A P-type a-Si (1-x-y) C x N y was obtained similarly by subjecting silane diluted with hydrogen, methane (CH₄), ammonia (NH₃) and diborane (B₂H₆) (B/(Si+C+N)=0.50 atom %] to the glow discharge decomposition. In that case, the gas composition involved in the glow discharge decomposition was adjusted so that the atomic fraction (x+y) in the formula: a-Si (1-x-y) C x N y , would fall in the range of from 0.80 to 0.05. A solar cell was constructed by successively depositing the P-type a-Si (1-x-y) C x N y , the I-type a-Si and the N-type a-Si in the order mentioned on the SnO₂ film of 25 Ω/□ and finally vacuum depositing aluminum of 3.3 mm². During the glow discharge, the temperature of the substrate was kept at 250°C. The thickness of the I-layer was 500 nm (5,000 Å), the thickness of the N-layer was 50 nm (500 Å) and the thickness of the P-type a-Si (1-x-y) C x N y layer was 13.5 nm (135 Å). This solar cell was tested for cell properties by use of a AM-1 solar simulator made by Ushio Electric Industry Co., Ltd. under a solar illumination power of 100 mW/cm². The characteristics of the obtained solar cells having a construction of glass/SnO₂/P-type a-Si (1-x-y) C x N y :H/I-type a-Si:H/N-type a-Si:H/Al are shown in Table 1 with respect to varied compositions of the P-type a-Si (1-x-y) C x N y . It is seen in Table 1 that the conversion efficiency which is 4.6% for the P-layer made from silane alone (i.e. P-type a-Si:H) is increased to 6.5% even when the values of "x" and "y" in the amorphous semiconductor a-Si (1-x-y) C x N y :H of the present invention are 0.05 and 0.05 respectively, and is increased to 7.3% when "x" is 0.10 and "y" is 0.20, and is increased to 7.6% when "x" is 0.3 and "y" is 0.3, thus indicating that the amorphous silicon carbon nitride of the invention used as P-layer of PIN heterojunction solar cells permits a marked improvement in conversion efficiency as compared with the use of P-type a-Si:H. It should be noted here that while the increase in the short-circuit current density (Jsc) is naturally expected from the fact that the optical energy gap of the a-Si (1-x-y) C x N y is greater than that of the a-Si, the increase in the open circuit voltage (Voc) is quite beyond expectation. The conspicuous improvement in the conversion efficiency is attained by the improvement in these two factors. Substantially the same results were obtained when SiF₄, CH₄ and NH₃ were used instead. The optical energy gap (Eg.opt) of the a-Si (1-x-y) C x N y is higher than that of the a-Si as shown in Table 1, and accordingly the use of the amorphous semiconductor of the invention as window materials is naturally expected to bring about an improvement in short-circuit current density (Jsc). Moreover, it brings about an unexpected conspicuous improvement in open circuit voltage (Voc). The reason therefor evidently exists in the relation between the diffusion potential (Vd) and the open circuit voltage (Voc), which plots in a straight line, as shown in Fig. 3. This means that the value of Voc linearly increases in proportion to the increase of Vd. This fact indicates that the diffusion potential is enhanced and Voc is proportionately improved by using an amorphous semiconductor having a large optical energy gap as a material for the window of the PIN junction photovoltaic device. As described above, when the amorphous semiconductor having an Eg.opt of at least about 1.85 eV and a PIN junction diffusion potential (Vd) of at least 1.1 volts is employed as a window material of a heterojunction photovoltaic device, marked improvements are obtained in not only Jsc, but also Voc. The same result is obtained also in the case where the N-type a-Si (1-x-y) C x N y is used as a N-layer of photovoltaic device of the type that the light impinges on the N-layer side, as shown in Fig. 1(b).

Claims: An amorphous silicon carbon nitride semiconductor having the general formula: a-Si (1-x-y) C x N y which is doped with a P-type or N-type impurity which is not nitrogen and having an electric conductivity of not less than 10⁻⁸ (Ω cm)⁻¹ and the doped amorphous silicon carbon nitride containing in addition hydrogen and/or fluorine. Amorphous silicon alloy PIN junction photovoltaic device, wherein at least one of the P-type and N-type amorphous silicon semiconductors is an amorphous silicon carbon nitride semiconductor having the general formula: a-Si (1-x-y) C x N y which is doped with a P-type or N-type impurity which is not nitrogen and having an electric conductivity of not less than 10⁻⁸ (Ωcm)⁻¹ and the doped amorphous silicon carbon nitride containing in addition hydrogen and/or fluorine. The photovoltaic device of claim 2, wherein the values, x and y, in the general formula satisfy the following equations: 0.05 ≦ x ≦ 0.75; 0.05 ≦ y ≦ 0.75 and 0.10 ≦ x+y ≦ 0.80.

Inventors: YOSHIHIRO, HAMAKAWA, YOSHIHISA, TAWADA
Applicants: KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA
Application year: 1982
Main classification: H01L31
IPC codes: H01L31