JP2000252497A - Method for manufacturing thin-film photoelectric conversion device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily manufacturing a thin-film photoelectric conversion device with improved photoelectric conversion characteristics. SOLUTION: When manufacturing a silicon thin-film photoelectric conversion device by successively forming a reverse-side metal electrode 102, a reverse-side transparent conductive film 103, and a thin-film photoelectric conversion unit 11, and a transparent electrode 2 on a substrate 1, a reverse-side transparent conductive film is formed for 1-30 seconds by the pressure in a reaction chamber that is equal to or more than 5×10-2 Torr at the initial stage of film formation, then the pressure in the reaction chamber is reduced to 1/10 or less of the pressure at the initial stage of film formation, and the remaining reverse-side transparent conductive film is formed when forming the reverse-side transparent conductive film 103 to 10 nm-1 μm by the sputtering method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a thin film photoelectric conversion device, and more particularly to a method for improving characteristics of a manufactured thin film photoelectric conversion device. In the specification of the present application, the terms “crystalline” and “microcrystal” also mean a case where the material partially contains an amorphous material.

[0002]

2. Description of the Related Art In recent years, photoelectric conversion devices using semiconductor thin films have been vigorously developed. In the development of these photoelectric conversion devices, the objective is to achieve both low cost and high performance by forming a high-quality semiconductor thin film on an inexpensive substrate by a low-temperature process. Such a photoelectric conversion device,
It is expected to be applied to various uses such as solar cells and optical sensors.

As an example of a photoelectric conversion device, a back metal electrode, a back transparent conductive film, a thin film photoelectric conversion unit,
And those having a structure in which transparent electrodes are sequentially laminated. The back transparent conductive film between the back metal electrode and the thin film photoelectric conversion unit relaxes the thermal strain due to the difference in the coefficient of thermal expansion between the metal electrode and the semiconductor thin film to increase the adhesion, and the metal atoms contain the thin film photoelectric conversion unit. It is provided to prevent diffusion to the surface. This transparent conductive film on the back is generally 1
It has high transmittance at a thickness of 0 nm to 1 μm.
It is required to have a low resistivity of 5 × 10 ⁻³ Ωcm or less. In order to form a rear transparent conductive film satisfying such conditions, for example, 2 × 10 ⁻² Torr by using a sputtering method.
r or lower, base temperature of 100 to 450 ° C, 500 to
The condition of 1500 mW / cm ² of discharge power is adopted.

However, it has been found that when the transparent conductive film on the back surface is formed under the above film forming conditions, the photoelectric conversion characteristics of the manufactured photoelectric conversion device are not sufficiently improved.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for easily manufacturing a thin film photoelectric conversion device having improved photoelectric conversion characteristics.

[0006]

Means for Solving the Problems The inventors of the present invention adopt a general condition that has been frequently used in forming a back transparent conductive film by a sputtering method. ^- ), The back metal electrode is damaged and the surface of the back metal electrode is oxidized, and the photoelectric conversion characteristics of the resulting photoelectric conversion device cannot be sufficiently improved.

On the other hand, the present inventors formed a thin rear transparent conductive film by using a low damage condition only at the initial stage of the film formation when forming the rear transparent conductive film on the rear metal electrode by sputtering. Then, it has been found that a high-performance photoelectric conversion characteristic can be obtained by forming a back transparent conductive film having the remaining thickness under the condition that a high-quality film can be obtained.

According to a first method of manufacturing a thin film photoelectric conversion device of the present invention, a back metal electrode, a back transparent conductive film, a thin film photoelectric conversion unit, and a transparent electrode are sequentially formed on a substrate to manufacture a thin film photoelectric conversion device. When forming the transparent conductive film on the back surface by sputtering, 5 × 10
After forming the back transparent conductive film at a reaction chamber pressure of ^-2 Torr or more for 1 to 30 seconds, the pressure in the reaction chamber is reduced to 1/10 or less of the initial film formation to form the remaining thickness of the back transparent conductive film. It is characterized by forming a film.

According to a second method of manufacturing a thin film photoelectric conversion device of the present invention, a back metal electrode, a back transparent conductive film, a thin film photoelectric conversion unit, and a transparent electrode are sequentially formed on a substrate to manufacture the thin film photoelectric conversion device. In forming the back transparent conductive film by sputtering, 80 to 5
After forming the back surface transparent conductive film at a discharge power of 00 mW / cm ² for 1 to 30 seconds, the discharge power was increased to 4 in the initial stage of film formation.
The method is characterized in that the back surface transparent conductive film having the remaining thickness is formed by increasing the thickness twice or more.

According to a third method of manufacturing a thin film photoelectric conversion device of the present invention, a back metal electrode, a back transparent conductive film, a thin film photoelectric conversion unit, and a transparent electrode are sequentially formed on a substrate to manufacture the thin film photoelectric conversion device. When forming the transparent conductive film on the back surface by sputtering, 100 ° C.
After forming the back transparent conductive film at the following film forming temperature for 1 to 30 seconds, the film forming temperature is raised to 100 ° C. or more, and the back transparent conductive film having the remaining thickness is formed.

In the present invention, the material of the back transparent conductive film is not particularly limited as long as it is a transparent conductive oxide (TCO), but it is preferable to use a film containing ZnO as a main component.

In the present invention, as the back metal electrode,
At least one selected from the group consisting of Ag, Al, Au, Cu, Pt and alloys thereof is used.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, as the photoelectric conversion unit, for example, a photoelectric conversion unit including an amorphous silicon-based photoelectric conversion layer, a photoelectric conversion unit including a crystalline silicon-based photoelectric conversion layer, and one or more amorphous silicon-based photoelectric conversion units A tandem-type photoelectric conversion unit in which a photoelectric conversion layer and one or more crystalline silicon-based photoelectric conversion layers are stacked, CdS
/ CdTe photoelectric conversion unit including photoelectric conversion layer, Cu
Examples include a photoelectric conversion unit including an InS ₂ -based photoelectric conversion layer. Hereinafter, the present invention will be described in more detail by taking a silicon-based thin-film photoelectric conversion unit as an example.

An example of the silicon-based thin-film photoelectric conversion device according to the present invention will be described with reference to the sectional view shown in FIG. The silicon-based thin-film photoelectric conversion device includes a composite electrode 10 including an adhesion-imparting film 101, a back metal electrode 102, and a back transparent conductive film 103 on a substrate 1, and a layer of one conductivity type (for example, n
Layer) 111, a photoelectric conversion unit 11 including a crystalline silicon-based photoelectric conversion layer (i-layer) 112 substantially composed of an intrinsic semiconductor and an opposite conductivity type layer (for example, a p-layer) 113, a transparent electrode 2, a comb-shaped metal It has a structure in which electrodes 3 are sequentially laminated. Light hν to be subjected to photoelectric conversion enters this photoelectric conversion device from the transparent electrode 2 side.

As the substrate 1, a metal such as stainless steel, an organic film, ceramics, or low-melting-point inexpensive glass can be used.

A composite electrode 10 including an adhesion-imparting film 101, a back metal electrode 102, and a back transparent conductive film 103 is formed on a substrate 1. The adhesion-imparting film 101 is not necessarily provided, but by providing the adhesion-imparting film 101, the adhesion between the substrate 1 and the back metal electrode 102 can be improved. 20 to 20
For example, Ti having a thickness of 50 nm is used. Such a Ti layer is formed, for example, by vapor deposition or sputtering. Ag, Au, A
It is preferable to use a metal selected from the group consisting of l, Cu and Pt, or an alloy thereof. The back metal electrode 102 is formed by a method such as vacuum evaporation or sputtering. For example, the base temperature is set to 100 to 330 ° C., more preferably 200 to 300 ° C., and an Ag layer having high light reflectivity is formed by vacuum deposition.

The uneven structure on the upper surface of the back metal electrode 102 can be formed by various methods. For example, it can also be changed by changing the temperature conditions and the like when forming the metal electrode. Further, a method of forming an uneven structure on the surface of the substrate 1 by etching or the like, forming a thin back metal electrode 102 thereon, and forming the surface of the back metal electrode 102 into an uneven structure along the uneven structure of the substrate 1 is known. No. In addition, a transparent conductive oxide layer (not shown) having an uneven surface is deposited on the substrate 1, a thin back metal electrode 102 is formed thereon, and the surface of the back metal electrode 102 is A method of forming an uneven structure along the uneven structure of the layer may be used.

The back transparent electrode formed on the back metal electrode 102
The bright conductive film 103 is made of ITO, SnO _Two, ZnO etc.
It is preferable to form at least one or more selected layers.
In particular, a film containing ZnO as a main component is particularly preferable.
No. The average crystal grain size of the back transparent conductive film 103 is 100 nm.
It is preferable that it is above. Also, the back transparent conductive film 10
3 preferably has a thickness of 10 nm to 1 μm,
Further, the thickness is preferably 50 nm to 1 μm.
1.5 × 10^-3It is preferably Ωcm or less.
As mentioned above, the back transparent conductive material that satisfies these conditions
Conventionally, 2 × 10^-2Pressure below Torr
Force, base temperature of 100-450 ° C, 500-1500m
W / cm^TwoThe sputtering condition of discharge power is adopted
However, under these conditions, the photoelectric conversion characteristics were not sufficiently improved.
You.

In the present invention, by using a low-damage conditions during sputtering of the back transparent conductive film, the negative ions generated in accordance with the sputtering ^- by (O, etc.), it is possible to suppress the damage to the back metal electrode In addition, the oxidation of the surface of the back metal electrode is reduced. However, the film quality (resistivity, transmittance) of the rear transparent conductive film is deteriorated only under the low damage condition, and the photoelectric conversion characteristics are not improved. Therefore, in the present invention, a thin rear transparent conductive film is formed on the surface of the rear metal electrode using low damage conditions only at the initial stage of film formation, and then the remaining transparent conductive film of the remaining thickness is formed under the condition that a high quality film is obtained. The formation reduces the damage of the photoelectric conversion unit and improves the photoelectric conversion characteristics of the finally obtained photoelectric conversion device.

Specific methods for forming the back transparent conductive film include the following methods (1) to (3).

(1) After forming a backside transparent conductive film at a reaction chamber pressure of 5 × 10 ⁻² Torr or more for 1 to 30 seconds at the initial stage of film formation, the pressure in the reaction chamber is reduced to 1/10 or less of the initial stage of film formation. A method of forming a lower-surface transparent conductive film with the remaining thickness lowered. In this method, the pressure in the reaction chamber at which a high-quality film of the second stage can be obtained is 2 × 10 ⁻² Torr or less, preferably on the order of 10 ⁻³ Torr.

(2) 80 to 500 mW / cm at the beginning of film formation
After forming the back transparent conductive film with discharge power of ² for 1 to 30 seconds, the discharge power is increased to four times or more of the initial stage of film formation, and the remaining thickness of the back transparent conductive film is formed. In this method, the condition of the discharge power to obtain a high quality film of the second stage is 500 to 1500 mW / cm ² .

(3) After forming the transparent conductive film on the back surface at a film formation temperature (base temperature) of 100 ° C. or less for an initial period of 1 to 30 seconds, the film formation temperature (base temperature) is raised to 100 ° C. or more. To form a transparent conductive film on the backside with the remaining thickness. In this method, the condition of the film formation temperature (base temperature) at which a high-quality film of the second stage is obtained is 100 to 450 ° C., and more preferably 100 to 300 ° C.

In any of the following methods, a back transparent conductive film of 1 to 10 nm is formed by forming a film for 1 to 30 seconds under initial conditions for film formation (low damage condition). Further, since the initial condition (low damage condition) can be easily changed from the initial condition (low damage condition) to the second stage condition (high quality film forming condition), the workability between the conventional manufacturing method and the manufacturing method of the present invention can be improved. There is little difference. Furthermore, the above (1)
It goes without saying that the back surface transparent conductive film may be formed by combining the methods (3) to (3).

The photoelectric conversion unit 11 is provided on the composite electrode 10.
Is formed. All the semiconductor layers included in the photoelectric conversion unit 11 are deposited by the plasma CVD method with the base temperature set at 400 ° C. or lower. Plasma CVD
The method is generally well-known parallel plate type RF.
Plasma CVD may be used or at a frequency of 150 MHz.
Plasma CVD using a high-frequency power supply in the following RF band to VHF band may be used.

The photoelectric conversion unit 11 has a one conductivity type layer 11
1, a photoelectric conversion layer 112 and a reverse conductivity type layer 113 are included. One conductivity type layer 111 may be an n-type layer or a p-type layer, and correspondingly, reverse conductivity type layer 113 may be a p-type layer or an n-type layer. The photoelectric conversion layer 112 is substantially made of a non-doped intrinsic semiconductor. However, since a p-type layer is usually arranged on the light incident side in the photoelectric conversion device, the one conductivity type layer 111 is generally an n-type layer and the opposite conductivity type layer 113 is a p-type layer in the structure of FIG. is there.

On the back transparent conductive film 103, one conductive type layer 1 is formed.
11 is formed. One conductivity type layer 111 is made of, for example, an n-type silicon-based thin film doped with phosphorus as a conductivity type determining impurity atom. However, the impurity atoms are not particularly limited, and may be nitrogen or the like in the n-type layer. In addition, one conductivity type layer 1
The semiconductor material of No. 11 is not particularly limited, and amorphous silicon, an alloy material such as amorphous silicon carbide or amorphous silicon germanium, polycrystalline silicon, microcrystalline silicon partially containing amorphous, or an alloy material thereof can also be used. If necessary, the crystallization fraction and the carrier concentration can be controlled by irradiating the deposited one-conductivity-type layer 111 with pulsed laser light (laser annealing).

On the one conductivity type layer 111, a crystalline (polycrystalline or microcrystalline) silicon-based photoelectric conversion layer 112 substantially composed of a non-doped intrinsic semiconductor is deposited. As the crystalline (polycrystalline or microcrystalline) silicon-based photoelectric conversion layer, a polycrystalline silicon film or a microcrystalline silicon film having a volume crystallization fraction of 80% or more or a weak p-type or It is possible to use a silicon-based thin film material that is weak n-type and has a sufficient photoelectric conversion function. The semiconductor material forming the photoelectric conversion layer 112 is not particularly limited, and an alloy material such as silicon carbide or silicon germanium can be used.

The thickness of the photoelectric conversion layer 112 is generally 0.5 to 20 so that necessary and sufficient photoelectric conversion can be performed.
It is formed in the range of μm. In addition, when the crystalline silicon-based photoelectric conversion layer is formed at a low temperature of 400 ° C. or lower, a large amount of hydrogen atoms that terminate and inactivate defects at crystal grain boundaries and grains are included. Specifically, the hydrogen content of the photoelectric conversion layer is in the range of 1 to 30 atomic%. Furthermore, many of the crystal grains contained in the crystalline silicon-based photoelectric conversion layer extend upward from the underlayer in a columnar shape, and have a (110) preferential crystal orientation plane parallel to the film surface. And
(11) for the (220) diffraction peak in X-ray diffraction
1) The intensity ratio of the diffraction peak is 0.2 or less.

On the photoelectric conversion layer 112, a layer 113 of the opposite conductivity type is provided.
Is formed. The opposite conductivity type layer 113 is made of, for example, a p-type silicon-based thin film doped with boron as a conductivity type determining impurity atom. However, the impurity atoms are not particularly limited, and may be aluminum or the like in the case of a p-type layer. As the semiconductor material of the opposite conductivity type layer 113, amorphous silicon, an alloy material such as amorphous silicon carbide or amorphous silicon germanium, polycrystalline silicon, microcrystalline silicon partially containing amorphous, or an alloy material thereof is used. Can also.

[0031] Here, even when the surface of the composite electrode 10 is substantially flat, the surface T _B of the photoelectric conversion unit 11 which is deposited thereon exhibits a textured surface structure including fine unevenness. Further, if the surface T _A of the composite electrode 10 has a surface texture structure including irregularities, photoelectric conversion unit 1
1 of the surface T _B, as compared to the surface T _A of the composite electrode 10, the pitch of the unevenness in the texture structure is reduced. This is because a texture structure is generated based on the crystal orientation when the crystalline silicon-based photoelectric conversion layer 112 constituting the photoelectric conversion unit 11 is deposited. Therefore the surface T _B of the photoelectric conversion unit 11 becomes a fine surface irregularities textured structure suitable to reflect light of a wide range of wavelength regions, the greater the light confinement effect in the photoelectric conversion device.

The transparent electrode 2 is formed on the photoelectric conversion unit 11 as a front electrode. This transparent electrode 2 is made of IT
1 selected from the group consisting of O, SnO ₂ and ZnO
The transparent conductive oxide (TCO) is formed of the above. Further, a comb-shaped metal electrode (grid electrode) is formed on the transparent electrode 2.
3 is formed. This comb-shaped metal electrode 3 is made of Al, Ag,
It is formed of a metal selected from the group consisting of Au, Cu and Pt, or an alloy thereof.

[0033]

Embodiments of the present invention will be described below.

Example 1 A polycrystalline silicon photoelectric conversion device shown in FIG. 1 was manufactured. First, the composite electrode 10 was formed on the glass substrate 1. This composite electrode 10 has a thickness of 2
Adhesion-imparting film 101 made of 0 nm Ti, thickness 300
back metal electrode 102 made of Ag having a thickness of 1 nm and a thickness of 1
Back transparent conductive film 1 made of 00 nm Al-doped ZnO
It consists of 03. Back metal electrode 102 made of Ag
Was deposited by vacuum evaporation. The back transparent conductive film 103 made of Al-doped ZnO was formed by the RF magnetron sputtering method under the following two-stage conditions. However, Ar gas was used as the sputtering gas,
0 ° C. and the RF power density of 850 mW / cm ² were not varied. First, 1 × 10 ⁻¹ To
Sputter for 10 seconds at rr reaction chamber pressure to a thickness of about 2n
m of ZnO was formed. Thereafter, the pressure in the reaction chamber was increased to 3 × 1
The film thickness of ZnO was reduced to 0 ^-3 Torr and the remaining thickness was formed.

Plasma CVD is performed on the composite electrode 10 described above.
The photoelectric conversion unit 11 including the one conductivity type layer (n layer) 111, the undoped crystalline silicon-based photoelectric conversion layer (i layer) 112, and the opposite conductivity type layer (p layer) 113 was formed by the method. The non-doped crystalline silicon-based photoelectric conversion layer 112 included in the photoelectric conversion unit 11 has a base temperature of 300 ° C.
And deposited to a thickness of 1.4 μm by RF plasma CVD. The hydrogen content of the photoelectric conversion layer 112 determined by secondary ion mass spectrometry was 2.3 atomic%, and the intensity ratio of the (111) diffraction peak to the (220) diffraction peak in X-ray diffraction was 0.084. Met. A transparent electrode 2 made of ITO having a thickness of 80 nm is formed on the photoelectric conversion unit 11 by sputtering.
And a comb-shaped metal electrode 3 for extracting current.

The short circuit current density when the light of AM 1.5 was incident on the obtained photoelectric conversion device at a light amount of 100 mW / cm ² was 22.8 mA / cm ² .

(Comparative Example 1) When the back transparent conductive film 103 made of Al-doped ZnO was formed by sputtering,
From the beginning to the end of film formation, the pressure in the reaction chamber is 3 × 10 ⁻³ To
The photoelectric conversion device shown in FIG. 1 was manufactured in the same manner as in Example 1 except that the pressure was set to a constant rr.

The short-circuit current density when the light of AM 1.5 was incident on the obtained photoelectric conversion device at a light quantity of 100 mW / cm ² was 22.1 mA / cm ² , which was lower than that of Example 1.

Next, FIG. 2 shows light absorption characteristics of the photoelectric conversion devices of Example 1 and Comparative Example 1. In this figure, the horizontal axis is the wavelength of light, and the vertical axis is the external quantum efficiency of the photoelectric conversion device. In addition, the dash-dot line curve and the solid line curve
5 shows spectral sensitivity characteristics of the photoelectric conversion devices of Example 1 and Comparative Example 1, respectively.

FIG. 2 shows that in the photoelectric conversion device of the first embodiment,
Compared with Comparative Example 1, the external quantum efficiency is particularly high in the wavelength region of 500 to 600 nm. This is Al
This is an effect obtained by forming the back transparent conductive film 103 made of doped ZnO in two stages: a low damage condition capable of reducing damage and oxidation of the back metal electrode, and a condition capable of forming a high quality film.

Example 2 The photoelectric conversion shown in FIG. 1 was performed in the same manner as in Example 1 except that the back transparent conductive film 103 made of Al-doped ZnO was formed by RF magnetron sputtering under the following two-stage conditions. The device was manufactured. However, Ar gas was used as the sputtering gas,
0 ° C. and the pressure in the reaction chamber, 3 × 10 ⁻³ Torr, were not changed and kept constant. First, 200 mW / c at the beginning of film formation
Sputtering at RF power density of m ² for 10 seconds to a thickness of about 2n
m of ZnO was formed. Thereafter, the RF power density was increased to 850.
The film thickness was increased to mW / cm ² , and the remaining thickness of ZnO was deposited.

The short-circuit current density when light of AM 1.5 was incident on the obtained photoelectric conversion device at a light amount of 100 mW / cm ² was 22.5 mA / cm ² .

Example 3 The photoelectric conversion shown in FIG. 1 was performed in the same manner as in Example 1 except that the back transparent conductive film 103 made of Al-doped ZnO was formed by RF magnetron sputtering under the following two-stage conditions. The device was manufactured. However, Ar gas was used as a sputtering gas, the reaction chamber pressure was 3 × 10 ⁻³ Torr, and the RF power density was 850 mW / c.
m ² is not changed and kept constant. First, at the initial stage of film formation, sputtering is performed for 10 seconds at a base temperature of 50 ° C. to a thickness of about 2 nm.
Was formed. Thereafter, the base temperature was raised to 150 ° C., and a ZnO film having the remaining thickness was formed.

The short-circuit current density when light of AM 1.5 was incident on the obtained photoelectric conversion device at a light quantity of 100 mW / cm ² was 22.9 mA / cm ² .

[0045]

As described above in detail, according to the present invention, it is possible to provide a method for easily manufacturing a silicon-based thin film photoelectric conversion device having improved photoelectric conversion characteristics.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a silicon-based thin-film photoelectric conversion device according to the present invention.

FIG. 2 is a diagram showing light absorption characteristics of the photoelectric conversion devices of Example 1 and Comparative Example 1.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate 10 ... Composite electrode 101 ... Adhesion imparting film, 102 ... Backside metal electrode, 103
... back transparent conductive film 11 ... photoelectric conversion unit 111 ... one conductivity type layer, 112 ... crystalline silicon-based photoelectric conversion layer, 113 ... reverse conductivity type layer 2 ... transparent electrode 3 ... comb-shaped metal electrode

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5F051 AA03 AA04 AA05 AA09 AA10 CB15 CB27 CB29 DA04 FA02 FA06 FA15 FA19 GA02 GA03 GA05

Claims (5)

[Claims] 1. A method of manufacturing a thin film photoelectric conversion device by sequentially forming a back metal electrode, a back transparent conductive film, a thin film photoelectric conversion unit, and a transparent electrode on a substrate, forming the back transparent conductive film by a sputtering method. When forming the film, after forming the backside transparent conductive film at a reaction chamber pressure of 5 × 10 ⁻² Torr or more for 1 to 30 seconds at the initial stage of the film formation, the pressure in the reaction chamber is reduced to 1/10 or less of the initial stage of the film formation. A method of manufacturing a thin film photoelectric conversion device, wherein a back transparent conductive film having a remaining thickness is formed. 2. A method for manufacturing a thin film photoelectric conversion device by sequentially forming a back metal electrode, a back transparent conductive film, a thin film photoelectric conversion unit, and a transparent electrode on a substrate, forming the back transparent conductive film by a sputtering method. At the time of film formation, after forming a back surface transparent conductive film for 1 to 30 seconds with a discharge power of 80 to 500 mW / cm ^{2 at} the initial stage of film formation, the discharge power is increased to 4 times or more of the initial film formation and the remaining thickness is increased. A method for manufacturing a thin-film photoelectric conversion device, comprising: forming a transparent conductive film on the back surface. 3. A backside transparent conductive film is formed by a sputtering method when a backside metal electrode, a backside transparent conductive film, a thin film photoelectric conversion unit, and a transparent electrode are sequentially formed on a substrate to manufacture a thin film photoelectric conversion device. When forming a film, a backside transparent conductive film is formed at a film formation temperature of 100 ° C. or less at an initial stage of film formation for 1 to 30 seconds, and then the film formation temperature is increased to 100 ° C. or more and the remaining thickness of the back surface transparent conductive film is A method for manufacturing a thin film photoelectric conversion device, comprising forming a film. 4. The method for manufacturing a thin-film photoelectric conversion device according to claim 1, wherein the back transparent conductive film is a film containing ZnO as a main component. 5. The method according to claim 1, wherein the back metal electrode is made of Ag, Al, A
4. The method for manufacturing a thin-film photoelectric conversion device according to claim 1, comprising at least one selected from the group consisting of u, Cu, Pt and an alloy thereof.