JP5559620B2 - Substrate with transparent conductive film - Google Patents

Description

  The present invention relates to a substrate with a transparent conductive film suitable for manufacturing, for example, a thin film solar cell, and more particularly to a substrate with a transparent conductive film in which the moisture resistance of a zinc oxide transparent conductive film is improved.

  In recent years, among photoelectric conversion devices, thin film photoelectric conversion devices that require less raw materials in order to achieve both low cost and high efficiency of photoelectric conversion devices including solar cells have attracted attention and have been vigorously developed. Yes. In particular, a method of forming a high-quality semiconductor layer on an inexpensive substrate such as glass using a low-temperature process is expected as a method capable of realizing low cost.

  Generally, in order to form a thin film photoelectric conversion device, it is indispensable to provide a transparent electrode layer in a part thereof. The thin film photoelectric conversion device is formed including one or more photoelectric conversion units between the transparent electrode layer and the back electrode layer, and light is incident from the transparent electrode layer side.

For the transparent electrode layer, for example, a transparent conductive oxide (hereinafter also referred to as TCO) such as tin oxide (SnO ₂ ) and zinc oxide (ZnO) is used. Generally, chemical vapor deposition (CVD), sputtering is used. And formed by a method such as vacuum deposition. The transparent electrode layer used in the thin film photoelectric conversion device desirably has an effect of increasing the scattering of incident light by having fine irregularities on the surface. This is because the thin film photoelectric conversion device can make the photoelectric conversion layer thinner compared to the conventional photoelectric conversion device using bulk single crystal or polycrystalline silicon. There is a problem that it is limited by the film thickness. Therefore, in order to use light incident on the photoelectric conversion unit including the photoelectric conversion layer more effectively, the surface of the transparent electrode layer or metal layer in contact with the photoelectric conversion unit is made uneven (textured), and light is transmitted at the interface. After scattering, the optical path length is extended by making it enter into a photoelectric conversion unit, and the device which makes the light absorption amount in a photoelectric converting layer increase is made | formed. This technique is called “optical confinement”, and is an important elemental technique for practical use of a thin film photoelectric conversion device having high photoelectric conversion efficiency.

  The photoelectric conversion unit is composed of a pn junction or pin junction semiconductor layer. When a pin junction is used for a photoelectric conversion unit, a p-type layer, an i-type layer, and an n-type layer are laminated in this order or vice versa, and the i-type photoelectric conversion layer that occupies the main part is amorphous. One is called an amorphous photoelectric conversion unit, and one whose i-type layer is crystalline is called a crystalline photoelectric conversion unit. For the semiconductor layer, amorphous silicon, crystalline silicon, or the like is used as a silicon-based thin film semiconductor.

  A silicon-based thin film photoelectric conversion device, which is an example of a thin film photoelectric conversion device, usually has a pin junction composed of a p-type layer, a substantially intrinsic photoelectric conversion layer, and an n-type layer on a photoelectric conversion unit. Used. Among these, those using amorphous silicon for the i-type layer are called amorphous silicon photoelectric conversion units, and those using crystalline silicon are called crystalline silicon photoelectric conversion units. Note that as the amorphous or crystalline silicon-based material, not only a case where only silicon is used as a main element constituting a semiconductor, but also an alloy material including elements such as carbon, oxygen, nitrogen, germanium, and the like can be used. The main constituent material of the conductive layer is not necessarily the same as that of the i-type layer. For example, amorphous silicon carbide can be used for the p-type layer of the amorphous silicon photoelectric conversion unit, and n A silicon layer containing crystalline material in the mold layer (also called microcrystalline silicon) can be used.

  As a method for improving the conversion efficiency of a thin film photoelectric conversion device, a thin film photoelectric conversion device employing a structure called a stacked type in which two or more photoelectric conversion units are stacked is known. In this method, a front photoelectric conversion unit including a photoelectric conversion layer having a large optical forbidden band width (also referred to as a band gap) is disposed on the light incident side of the thin film photoelectric conversion device, and a small band gap is sequentially disposed behind the photoelectric conversion unit. By arranging the rear photoelectric conversion unit including the photoelectric conversion layer, photoelectric conversion over a wide wavelength range of incident light is enabled, and conversion efficiency of the entire apparatus is improved by effectively using incident light. . Among stacked thin film photoelectric conversion devices, a stack of an amorphous photoelectric conversion unit and a crystalline photoelectric conversion unit is referred to as a tandem thin film photoelectric conversion device. In the present application, the photoelectric conversion unit disposed relatively on the light incident side is referred to as a front photoelectric conversion unit, and the photoelectric conversion unit disposed adjacent to the side farther from the light incident side than this is rearward. It is called a photoelectric conversion unit.

As the back electrode layer formed on the photoelectric conversion unit, for example, a metal layer such as Al or Ag is formed by a sputtering method or a vacuum evaporation method. Further, a layer made of TCO such as indium tin oxide (ITO), SnO ₂ , or ZnO may be formed between the photoelectric conversion unit and the metal layer.

The thin film photoelectric conversion unit as described above is formed on a transparent electrode layer made of TCO such as SnO ₂ or ZnO. Among TCOs, SnO ₂ has been widely used as a transparent electrode layer. In recent years, ZnO, which is excellent in terms of transmittance for light in a long wavelength region, controllability of haze ratio as an index of light confinement effect, and reduction resistance to hydrogen radicals, has come to be used as a transparent electrode layer. I came.

  In general, a ZnO thin film used for a thin film photoelectric conversion device needs to be a polycrystalline thin film because it requires a surface uneven shape for exhibiting an “optical confinement” effect. On the other hand, the grain boundaries of polycrystalline ZnO hinder carrier transport (potential barrier), and the probability of crossing this barrier is proportional to the mobility, so the mobility tends to decrease as the barrier increases. It is known that there are many dangling bonds (also called dangling bonds) on the surface of the crystal grains, and there are gaps at the grain boundaries. For example, in the case of a polycrystalline metal, since the carrier movement is possible by the tunnel effect, it can be ignored. However, in polycrystalline ZnO, the dangling bond on the surface of the crystal grain is Zn or O, and the ionic bond Since the force is dominant, O is easily adsorbed on the dangling bond of Zn. In other words, since ZnO has a dominant ion binding force and oxygen adsorption and oxygen uptake into the film are remarkable, advanced film-forming techniques are required for the production of a polycrystalline ZnO thin film having high moisture resistance. .

  Non-Patent Document 1 clarifies that the temporal change of zinc oxide in a high-temperature and high-humidity environment is caused by the grain boundary scattering effect at the crystal grain boundary. That is, under high temperature and high humidity, oxygen adsorption to dangling bonds (oxygen vacancies) existing on the film surface and grain boundaries is promoted by high temperature steam. By this oxygen adsorption, the potential of ionized donors (positive ions) in the vicinity of the film surface extends to the inside of the film, preventing the movement of electrons. Non-Patent Document 1 states that moisture resistance can be improved by suppressing the spread of potential to the inside of the film by increasing the film thickness. However, in zinc oxide used for thin-film silicon-based solar cells, the unevenness on the film surface is intense to enhance the light confinement effect, and inevitably dangling bonds that exist on the film surface and grain boundaries increase. It tends to be difficult to improve moisture resistance. In particular, in a zinc oxide film formed at a low temperature using a low-pressure thermal CVD method, the crystal grain irregularities that grow naturally form a textured shape, and there are many gaps at the crystal grain boundaries in the film and their interfaces. The increase alone cannot secure sufficient moisture resistance. Therefore, it is required to control the fine structure in the zinc oxide film (crystal grain boundaries and defects at the interfaces).

  In general, the X-ray diffraction method is often used for crystal structure evaluation. With such an analytical evaluation method, crystal orientation, crystallite size, and the like can be evaluated. The crystal orientation indicates the orientation of crystal grains grown from various crystal nuclei (seed crystals) on the substrate, and indirectly indicates the denseness of the film. In addition, since the crystallite size is a single crystal component of the polycrystalline thin film, it indicates a minimum unit crystal grain boundary. That is, it is possible to indirectly evaluate the moisture resistance by the X-ray diffraction method. However, as described above, moisture resistance is thought to be caused by a decrease in oxygen adsorption to oxygen vacancies (defects in the film) existing on the film surface and grain boundaries. It can be said that direct evaluation is desirable.

Recently, an analysis method using Raman scattering spectroscopy has been reported as one of fine structure evaluations in a zinc oxide film. In Non-Patent Document 2, a defect is formed by implanting hydrogen ions into a single crystal ZnO with a hydrogen ion implantation apparatus, and analyzing the Raman spectrum before and after the implantation, the peak “A ₁ (LO ) ”. However, at present, there is no clear result that the A ₁ (LO) peak due to ion implantation is caused by oxygen deficiency.

Non-Patent Document 3 clarifies the relationship between the grain boundary scattering effect and the carrier concentration in a zinc oxide film formed at a low temperature by a low-pressure thermal CVD method. According to Non-Patent Document 3, when the carrier concentration exceeds 3 × 10 ²⁰ cm ⁻³ , carrier transport in the potential barrier of the crystal grain boundary becomes a phenomenon caused by the tunnel effect, and thus the influence of the grain boundary scattering effect is exerted. It is supposed to be significantly reduced. Therefore, when the carrier concentration exceeds 3 × 10 ²⁰ cm ⁻³ , resistance variation under a high temperature and high humidity environment can be reduced. However, since the increase in carrier concentration causes a decrease in transmittance in the infrared region, it can cause a decrease in performance in a multi-junction thin film silicon solar cell that requires light absorption up to the infrared region.

Thin Solid Film 516, 1314 (2008) Physical Review B 71,115213 (2005) Applied Physics Letters 90, 142107 (2007)

  The present invention provides a substrate with a transparent conductive film that has improved moisture resistance by controlling oxygen vacancies in a zinc oxide transparent conductive film, which is suitable as a substrate for a thin film photoelectric conversion device typified by, for example, a thin film silicon photoelectric conversion device. It is intended to provide.

  In view of the above problems, the present inventor has intensively studied. As a result, the present inventors have found that the problems can be solved by the following configuration, and have completed the present invention.

That is, the present invention includes, in order from the light incident side, and at least translucent substrate, a transparent substrate with a conductive film and a zinc oxide layer, a Raman spectrum peak intensity ratio of the zinc oxide E _{2 (high)} / A _{The present} invention relates to a substrate with a transparent conductive film, wherein ₁ (LO)> 2.0.

A preferred embodiment relates to the substrate with a transparent conductive film, characterized in that the Raman spectrum peak intensity ratio of the zinc oxide is E ₂ (high) / A ₁ (LO) ≧ 5.0.

The present invention provides a method of producing the transparent conductive film substrate with, by low-pressure thermal CVD method using at least water and diethyl zinc raw material, a flow rate ratio of water / diethyl zinc 2.0 or more on the permeability The present invention relates to a method for producing a substrate with a transparent conductive film , wherein a bulk zinc oxide layer is formed on a light-sensitive substrate . In one embodiment, after the bulk zinc oxide layer is formed, the outermost surface portion of the zinc oxide layer is formed at a water / diethyl zinc flow rate ratio of 2.0 or less.

  A preferred embodiment relates to the above-described method for producing a substrate with a transparent conductive film, wherein the outermost surface of a zinc oxide layer is subjected to a reducing plasma treatment.

  According to the present invention, it is possible to significantly improve the moisture resistance of a substrate with a transparent conductive film including a zinc oxide layer by quantifying and controlling oxygen vacancies that affect moisture resistance by a direct evaluation method. Thereby, the thin film photoelectric conversion device provided with the substrate of the present invention can exhibit excellent environmental reliability such as a small sheet resistance change rate.

It is a Raman spectrum figure concerning the example and comparative example of the present invention. It is a figure which shows the result of having evaluated the sheet resistance change rate before and behind the high temperature / humidity test which concerns on the Example and comparative example of this invention.

  Hereinafter, preferred embodiments of the present invention will be described.

  A well-known thing can be used for the said translucent board | substrate, for example, the plate-shaped member and sheet-like member which consist of glass, transparent resin, etc. are mainly used. In particular, it is preferable to use a glass substrate mainly as the light-transmitting substrate because of its high transmittance and low cost.

  Since the translucent substrate is located on the light incident side when the thin film photoelectric conversion device is configured, it is preferable that the translucent substrate is as transparent as possible in order to transmit more sunlight and absorb it in the photoelectric conversion unit. Also from the viewpoint, a glass plate is suitable as the material. From the same intention, in order to reduce the light reflection loss on the light incident surface of sunlight, it is desirable to apply a non-reflective coating to the light incident surface of the translucent substrate.

As the transparent electrode layer, a zinc oxide (ZnO) layer is used in the present invention. The zinc oxide layer may be any layer containing zinc oxide as a main component, but a binary compound is preferred. This is because in the case of many ternary compounds (for example, homologous compounds, Zn _m In ₂ O _{3 + m} ; m = 2 to 7), In atoms diffuse into the silicon layer during the silicon thin film deposition by the plasma CVD method, This is because metal deposition occurs in Moreover, B, Al, Ga, Si, Sc, F, etc. can be used as a dopant material which becomes an exogenous donor for controlling a carrier concentration. In the thin film photoelectric conversion device, since the transmittance in the infrared region having a wavelength of 800 nm or more is important, the carrier concentration of the zinc oxide layer is preferably 2 × 10 ²⁰ cm ⁻³ or less.

The present invention is characterized in that the Raman spectrum peak intensity ratio of the zinc oxide layer is E ₂ (high) / A ₁ (LO)> 2.0 from the viewpoint described later, and further the Raman spectrum. More preferably, the peak intensity ratio is E ₂ (high) / A ₁ (LO) ≧ 5.0. Here, the E ₂ (high) peak is a high-frequency E ₂ phonon mode having a Wurtzite structure and appears at 437 cm ⁻¹ , and the A ₁ (LO) peak is considered to be a peak derived from oxygen deficiency and is at 574 cm ⁻¹ . It is a peak that appears. The larger the E ₂ (high) peak is, the higher the crystallinity of zinc oxide is, and it has a dense microstructure. Further, the smaller the A ₁ (LO) peak, the fewer defects (dangling bonds) in the zinc oxide, and the oxidation reaction of the crystal grain boundaries due to the penetration of water or oxygen into the film can be suppressed. Thus, it is considered that the higher the E ₂ (high) / A ₁ (LO) peak, the higher the moisture resistance.

Raman scattering spectroscopy is a non-destructive analysis to know the structure and state of molecules using the difference between the frequency of Raman scattered light and the frequency of incident light (Raman shift) taking values specific to the structure of the material. It is used as a law. Recently, it has begun to be used for ZnO single crystal and polycrystalline bulk materials. For example, in Non-Patent Document 3, by the hydrogen ion implantation apparatus in a single crystal ZnO, intentionally performs defect formation, states that A ₁ peak is one due to a defect from the peak expression at that time. The present invention is based on the Raman scattering spectroscopy that can evaluate the microstructure (defects, etc.) and the knowledge that the moisture resistance is caused by the microstructure. This is because the ZnO thin film was evaluated using Raman scattering spectroscopy.

  The zinc oxide layer in the present invention can be manufactured using a film forming method such as a low pressure thermal CVD method, a sputtering method, a sol-gel method, or an ion plating method.

  In particular, since the low-pressure thermal CVD method can form a film at a low temperature of 200 ° C. or lower, there is an advantage that various substrates can be used, and it is an important length when forming a stacked thin film photoelectric conversion device. This is preferable because a zinc oxide layer having a surface texture structure useful for the light confinement effect in the wavelength region can be formed. When such a low-pressure thermal CVD apparatus is used, it is formed using diethyl zinc (DEZ), water, a doping gas, and a dilution gas as source gases under conditions where the substrate temperature is 150 ° C. or higher and the pressure is 5 to 1000 Pa. Can do.

The Raman spectrum intensity ratio of zinc oxide in the zinc oxide layer according to the present invention is E ₂ (high) / A ₁ (LO)> 2.0, preferably E ₂ (high) / A ₁ (LO) ≧ 5.0. In order to do this, for example, it can be controlled by adjusting the flow rate ratio of DEZ and water used in the source gas. For example, it is possible to increase the oxygen ratio in zinc oxide by making the flow rate of DEZ constant and increasing the flow rate of water. Specifically, the moisture resistance can be remarkably improved by increasing the H ₂ O / DEZ flow rate ratio to 2.0 or more, preferably 3.5 or more. On the other hand, it is possible to increase the zinc ratio by making the flow rate ratio of water constant and increasing the flow rate of DEZ. However, when the DEZ flow rate is changed, the film formation rate also changes, so it is more preferable to control the water flow rate in terms of film thickness control.

Generally, in the low-pressure thermal CVD method, the surface irregularity shape of zinc oxide that spontaneously changes is changed by changing the H ₂ O / DEZ flow rate ratio used as a raw material. In particular, since the surface shape of zinc oxide having the physical properties of the present invention has a sharper pyramid shape, it has hitherto been thought to cause a decrease in the performance of the stacked thin film photoelectric conversion device. However, as a result of intensive studies, the present inventor has clarified that the performance degradation is not caused by improving the manufacturing method of the photoelectric conversion device even in the substrate with the transparent conductive film having the physical properties.

For example, in the low pressure thermal CVD method, the H ₂ O / DEZ flow ratio when intentionally forming the outermost surface portion of the zinc oxide layer is preferably lowered to 2.0 or less, more preferably 1.75 or less. It is possible to loosen the pyramid shape . The outermost surface portion of the zinc oxide layer in here, refers to the vicinity of the interface consisting of a p-type semiconductor layer of the zinc oxide layer and the photoelectric conversion unit. In forming the translucent substrate near the bulk zinc oxide layer, H 2 _{O /} DEZ flow ratio, it is preferred in terms of transparency is 3.0 or more.

In addition to the above manufacturing method, the outermost surface of the zinc oxide layer is subjected to reducing plasma treatment such as B ₂ H ₆ / H ₂ before film formation of the power generation layer, so that the interface between the zinc oxide layer and the photoelectric conversion layer is performed. It is possible to improve the characteristics. For example, the processing conditions include a substrate temperature of 190 ° C., a high frequency power of 300 W, a pressure of 1.5 Torr, a B ₂ H ₆ flow rate of 20 sccm, a hydrogen flow rate of 5000 sccm, and a discharge time of 300 s. Good.

On the other hand, as a zinc component source gas, dimethyl zinc can be used in addition to diethyl zinc. Examples of the oxygen component source gas include oxygen, carbon dioxide, carbon monoxide, dinitrogen oxide, nitrogen dioxide, sulfur dioxide, dinitrogen pentoxide, alcohols (R (OH)), and ketones (R (CO)). R ′), ethers (ROR ′), aldehydes (R (COH)), amides ((RCO) _x (NH _3−x ), x = 1,2,3), sulfoxides (R (SO)) R ′) (wherein R and R ′ are alkyl groups). As the dilution gas, a rare gas (He, Ar, Xe, Kr, Rn), nitrogen, hydrogen, or the like can be used. As the doping gas, for example, diborane (B ₂ H ₆ ), alkylaluminum, alkylgallium, or the like can be used. For example, the gas composition ratio of B ₂ H _{6 to} DEZ is preferably 0.05 vol% or more. Since DEZ and water are liquids at normal temperature and normal pressure, they can be supplied after being vaporized by methods such as heat evaporation, bubbling, and spraying.

  In this invention, although the average film thickness of a zinc oxide layer is not limited, It is preferable that it is 500-4000 nm, and it is more preferable that it is 800-1900 nm. This is because if the ZnO film is too thin, it is difficult to sufficiently provide surface irregularities that effectively contribute to the light confinement effect, and it is difficult to obtain the necessary conductivity as a transparent electrode. This is because the light absorption by itself reduces the amount of light that passes through ZnO and reaches the photoelectric conversion unit, thereby reducing the conversion efficiency. Furthermore, when it is too thick, the film formation cost increases due to an increase in the film formation time.

  The surface unevenness of the zinc oxide layer has a haze ratio of about 10 to 50% in a state where the zinc oxide layer is formed on the translucent substrate in order to obtain a light confinement effect suitable for the thin film photoelectric conversion device. Is preferred. The average height difference of the surface unevenness of the zinc oxide layer having such a haze ratio is about 10 to 300 nm. If the surface unevenness of the zinc oxide layer is too small, sufficient light confinement effect cannot be obtained. Conversely, if the surface unevenness is too large, it may cause electrical and mechanical short circuit in the photoelectric conversion device. Therefore, the characteristics of the photoelectric conversion device may be deteriorated.

  Examples according to the present invention will be described below. The present invention is not limited to the following examples as long as the gist thereof is not exceeded.

(Comparative Example 1)
As Comparative Example 1 of the present invention, a zinc oxide layer on which a ZnO film having a Raman spectrum peak intensity ratio E2 (high) / A1 (LO) = 1.0 of the zinc oxide layer was formed. For the Raman spectrum, a microscopic Raman scattering spectrometer was used. Specifically, a zinc oxide layer having the Raman spectrum peak intensity ratio was formed on a translucent substrate having a thickness of 4 mm, 360 mm × 465 mm by a low pressure thermal CVD method. The zinc oxide layer was formed at a substrate temperature of 160 ° C., a pressure of 25 Pa, a vaporized DEZ (diethyl zinc) flow rate of 200 sccm, a vaporized water flow rate of 350 sccm, a diluted B ₂ H ₆ flow rate of 200 sccm, and a hydrogen flow rate of 400 sccm. The film thickness of the zinc oxide layer was 2300 nm, and the initial sheet resistance was 6Ω / □. The sheet resistance change rate (sheet resistance after test / sheet resistance before test) before and after the 85 ° C. and 85% RH environmental test of the produced transparent conductive film-attached substrate was 5.8.

Example 1
As Example 1 of the present invention, a zinc oxide layer on which a ZnO film having a Raman spectrum peak intensity ratio E2 (high) / A1 (LO) = 3.5 of the zinc oxide layer was formed was produced. Specifically, a zinc oxide layer having the Raman spectrum peak intensity ratio was formed on a translucent substrate having a thickness of 4 mm, 360 mm × 465 mm by a low pressure thermal CVD method. The zinc oxide layer was formed at a substrate temperature of 160 ° C., a pressure of 25 Pa, a vaporized DEZ flow rate of 200 sccm, a vaporized water flow rate of 600 sccm, a diluted B ₂ H ₆ flow rate of 200 sccm, and a hydrogen flow rate of 400 sccm. The film thickness of the zinc oxide layer was 2100 nm, and the initial sheet resistance was 6Ω / □. The sheet resistance change rate before and after the 85 ° C. and 85% RH environmental test of the produced substrate for a photoelectric conversion device was 2.5.

(Example 2)
As Example 2 of the present invention, a zinc oxide layer on which a ZnO film having a Raman spectrum peak intensity ratio E2 (high) / A1 (LO) = 5.0 of the zinc oxide layer was formed. Specifically, a zinc oxide layer having the Raman spectrum peak intensity ratio was formed on a translucent substrate having a thickness of 4 mm, 360 mm × 465 mm by a low pressure thermal CVD method. The zinc oxide layer was formed at a substrate temperature of 160 ° C., a pressure of 25 Pa, a vaporized DEZ flow rate of 200 sccm, a vaporized water flow rate of 700 sccm, a diluted B ₂ H ₆ flow rate of 200 sccm, and a hydrogen flow rate of 400 sccm. The film thickness of the zinc oxide layer was 1900 nm, and the initial sheet resistance was 6Ω / □. The sheet resistance change rate of the manufactured photoelectric conversion device substrate before and after the 85 ° C. and 85% RH environmental test was 1.3.

(Example 3)
As Example 3 of the present invention, a zinc oxide layer on which a ZnO film having a Raman spectrum peak intensity ratio E2 (high) / A1 (LO) = 7.0 of the zinc oxide layer was formed was produced. Specifically, a zinc oxide layer having the Raman spectrum peak intensity ratio was formed on a translucent substrate having a thickness of 4 mm, 360 mm × 465 mm by a low pressure thermal CVD method. The transparent electrode layer was formed at a substrate temperature of 160 ° C., a pressure of 25 Pa, a vaporized DEZ flow rate of 200 sccm, a vaporized water flow rate of 800 sccm, a diluted B ₂ H ₆ flow rate of 200 sccm, and a hydrogen flow rate of 400 sccm. The film thickness of the zinc oxide layer was 1700 nm, and the initial sheet resistance was 8Ω / □. The sheet resistance change rate of the produced photoelectric conversion device substrate before and after the 85 ° C. and 85% RH environmental test was 1.1.

  The result of Raman spectrum measurement is shown in FIG. 1, and the result of sheet resistance change rate is shown in FIG.

As a result of Comparative Example 1 and Example 1, the Raman spectrum peak intensity ratio E ₂ (high) / A ₁ (LO) of the zinc oxide layer was increased from 1.0 to 3.5, and 85 ° C., 85% RH. It indicates that the sheet resistance change rate before and after the environmental test can be reduced from 5.8 to 2.5, and the moisture resistance is improved. In addition, the results of Example 2 and Example 3 show that the Raman spectrum peak intensity ratio E ₂ (high) / A ₁ (LO) ≧ 5.0, and the sheet resistance change before and after the 85 ° C. and 85% RH environmental test. It is possible to make the ratio≈1, indicating that a substrate with a transparent conductive film having high moisture resistance and almost no change in sheet resistance can be realized.

Claims (5)

  In order from the light incident side, it is a substrate with a transparent conductive film comprising at least a light-transmitting substrate and a zinc oxide layer, and the Raman spectrum peak intensity ratio of the zinc oxide layer is E2 (high) / A1 (LO)> 2. A substrate with a transparent conductive film, characterized in that it is zero.   2. The substrate with a transparent conductive film according to claim 1, wherein a Raman spectrum peak intensity ratio of the zinc oxide layer is set to E2 (high) / A1 (LO) ≧ 5.0. A method of manufacturing a transparent substrate with a conductive film according to claim 1 or 2, the low-pressure thermal CVD method using at least water and diethyl zinc raw material, the flow rate ratio of water / diethyl zinc on 2.0 or more A method for producing a substrate with a transparent conductive film , wherein a bulk zinc oxide layer is formed on a translucent substrate. 4. The substrate with a transparent conductive film according to claim 3, wherein after forming the bulk zinc oxide layer, the outermost surface portion of the zinc oxide layer is formed at a flow rate ratio of water / diethyl zinc of 2.0 or less. Manufacturing method.   The method for producing a substrate with a transparent conductive film according to claim 3 or 4, wherein a reducing plasma treatment is performed on the outermost surface of the zinc oxide layer.

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