JP5563850B2 - Photoelectric conversion device and manufacturing method thereof - Google Patents

Description

  The present invention provides means capable of improving reliability and conversion efficiency in a photoelectric conversion device, and particularly relates to improvement of a back electrode portion of the photoelectric conversion device.

  In recent years, thin film solar cells, which are typical examples of photoelectric conversion devices (hereinafter also referred to as solar cells), have been diversified, and crystalline thin film solar cells have been developed in addition to conventional amorphous thin film solar cells. Solar cells are also in practical use. A thin film solar cell generally includes a light incident side transparent conductive layer, at least one photoelectric conversion unit, a back surface transparent conductive layer, and a back surface metal electrode layer, which are sequentially laminated on a light transmitting insulating substrate positioned on the light incident side. Contains. Each photoelectric conversion unit includes an i-type layer sandwiched between a p-type layer and an n-type layer.

  Most of the thickness of the photoelectric conversion unit is occupied by the i-type layer which is a substantially intrinsic semiconductor layer, and the photoelectric conversion action mainly occurs in the i-type layer. Therefore, the i-type layer, which is a photoelectric conversion layer, is preferably thicker for light absorption, but if it is thicker than necessary, the cost and time for deposition will increase. On the other hand, the p-type and n-type conductive layers serve to generate a diffusion potential in the photoelectric conversion unit, and the open circuit voltage (Voc), which is one of the important characteristics of the thin-film solar cell, depending on the magnitude of this diffusion potential. The value of depends on.

  However, these conductive layers are inactive layers that do not contribute to photoelectric conversion, and light absorbed by impurities doped in the conductive layers does not contribute to power generation and is lost. Therefore, it is preferable that the thicknesses of the p-type and n-type conductive layers be as thin as possible within a range that generates a sufficient diffusion potential.

  The above photoelectric conversion unit is an amorphous photoelectric conversion unit in which the i-type photoelectric conversion layer is amorphous regardless of whether the p-type and n-type conductivity type layers contained therein are amorphous or crystalline. The i-type layer is crystalline and is called a crystalline photoelectric conversion unit. Note that the term “crystalline” in the present invention includes those partially including an amorphous state as commonly used in the technical field of thin film photoelectric conversion devices.

  As an example of a thin film solar cell including an amorphous photoelectric conversion unit, an amorphous thin film silicon solar cell using amorphous silicon for an i-type photoelectric conversion layer can be given. An example of a thin film solar cell including a crystalline photoelectric conversion unit is a crystalline thin film silicon solar cell using microcrystalline silicon or polycrystalline silicon for an i-type photoelectric conversion layer.

  By the way, as a method of improving the conversion efficiency of a thin film solar cell, there is a method of stacking two or more photoelectric conversion units into a tandem type. In this method, a photoelectric conversion unit having a large band gap of the photoelectric conversion layer is disposed on the light incident side of the thin-film solar cell, and a photoelectric conversion unit having a small band gap of the photoelectric conversion layer is sequentially disposed behind the photoelectric conversion unit. Photoelectric conversion is enabled over a wide wavelength range of light, thereby improving the conversion efficiency of the entire solar cell. Among such tandem thin film solar cells, those including both an amorphous photoelectric conversion unit and a crystalline photoelectric conversion unit are sometimes referred to as hybrid thin film solar cells.

  For example, an amorphous silicon photoelectric conversion unit using i-type amorphous silicon with a wide band gap as a photoelectric conversion layer, and a crystalline silicon photoelectric conversion unit using i-type crystalline silicon with a narrow band gap as a photoelectric conversion layer In the hybrid thin-film solar cell in which the i-type amorphous silicon is laminated, the wavelength of light that can be photoelectrically converted by the i-type amorphous silicon is up to about 800 nm on the long-wavelength side, whereas the i-type crystalline silicon is longer than that. Since light up to about 1100 nm can be photoelectrically converted, a wider range of incident light can be effectively photoelectrically converted.

  In the thin film solar cell, in order to more effectively use the light incident on the photoelectric conversion unit, a back metal electrode layer made of a metal material having a high light reflectance is formed. Most of the light transmitted without being absorbed by the photoelectric conversion unit is reflected by the back surface metal electrode layer and re-enters the photoelectric conversion unit to perform photoelectric conversion. For this reason, it is desirable that the back surface metal electrode layer has a high reflectance, and materials having a high reflectance in the visible to near-infrared region are widely used.

  As a means for further improving the reflectance on the back electrode side, a photoelectric conversion device having a configuration in which a low refractive index layer is sandwiched between a back metal electrode layer and a back transparent conductive layer is known. In the case of this configuration, in order to obtain a sufficient reflectance enhancement effect, the film thickness of the low refractive index layer needs to be a certain level (for example, about 40 nm or more), but a material with a low refractive index is generally an insulator. Therefore, when a thick low refractive index layer is sandwiched between the back metal electrode layer and the back transparent conductive layer, the electrical junction between the back metal electrode layer and the back transparent conductive layer is deteriorated. There arises a problem of deterioration of solar cell characteristics. For this reason, for example, Patent Document 1 uses a low-refractive index layer having an opening, and Patent Document 2 uses a thin low-refractive index layer so that the reflectance is increased and the back metal electrode layer And an electrical connection between the transparent conductive layer on the back surface.

Japanese Patent Laid-Open No. 7-321362 JP 2007-266095 A

  However, the methods disclosed in Patent Document 1 and Patent Document 2 satisfy both the electrical connection between the back surface metal electrode layer and the back surface transparent conductive layer and the effect of improving the reflectance of the back surface electrode, and reliability. And there are problems with productivity.

  That is, in the method described in Patent Document 1, a mask vapor deposition method is used to form the opening of the low refractive index layer. According to this method, even in the portion shielded by the mask, the low refractive index material tends to adhere to the vicinity of the boundary of the mask opening due to the wraparound. For this reason, when the area of the opening is reduced, the ratio of the boundary portion where the low refractive index material adheres to the mask opening increases, and the adverse effect on the electrical connection between the back surface metal electrode layer and the back surface transparent conductive layer is remarkable. Appears easily. In order to obtain a sufficient reflectance enhancement effect by providing the low refractive index layer, it is desirable to reduce the aperture ratio. Here, when the interval between the openings is increased, the loss due to the resistance of the back surface transparent conductive layer cannot be ignored. Therefore, when a low refractive index layer having an opening is used, it is necessary to pay special attention to the formation method and arrangement of the opening and the actual shape. In addition, when a low refractive index layer is formed, there is a problem that productivity is lowered because a mask is used. Furthermore, the thickness of the low refractive index layer is as thick as 80 nm, and the light enhancement of the low refractive index layer itself may impair the reflectance enhancement effect.

  Further, in the case of the solar cell disclosed in Patent Document 2, it is considered that the low refractive index layer is made of a low refractive index material formed in a layer shape, and since the film thickness of the low refractive index layer is thin, sufficient reflectance is obtained. In addition to the problem that the enhancement effect is difficult to obtain, a layered insulator is sandwiched between the back transparent conductive layer and the back metal electrode layer, making it inherently difficult to ensure a stable electrical connection. There is a problem of becoming.

  Furthermore, Ag, which is one of the materials having the highest reflectance with respect to light in the visible to infrared region, is widely used as the back metal electrode layer material. In general, Ag has low adhesion strength, and in a configuration in which a low refractive index layer is sandwiched between a back metal electrode layer made of Ag and a back transparent conductive layer as disclosed in Patent Document 1 and Patent Document 2, There is a problem that the back metal electrode layer is easily peeled off due to insufficient adhesion strength.

    An object of the present invention is to provide a photoelectric conversion device that is highly reliable and has high conversion efficiency, in which a back surface metal electrode layer hardly peels off in the photoelectric conversion device.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by the following configuration, and have completed the present invention.

That is, the present invention relates to the following.
At least a photoelectric conversion unit, a back surface transparent conductive layer, an island-shaped low refractive index material having a refractive index smaller than that of the back surface transparent conductive layer in a wavelength region where the photoelectric conversion unit has sensitivity, and a back surface metal electrode layer. a sequentially and a low refractive index material and the back metal electrode layer is in direct contact, the thickness of the low refractive index material Ri der than 10nm or less 1 nm, that have a width is formed in an island-like 0.01μm~50μm A photoelectric conversion device characterized by that.
The photoelectric conversion device as described above, wherein the low refractive index material contains LiF or MgF ₂ .
The photoelectric conversion device as described above, wherein a portion of 30% to 90% of the surface of the back transparent conductive layer is covered with a low refractive index material .
Back side transparent conductive layer, In, Zn, Al, Ga , photoelectric conversion device above consists oxide containing a constituent element at least one of B.
The back transparent conductive layer has a concavo-convex structure on the surface on the island-shaped low refractive index material layer forming side, and the low refractive index material layer is formed into an island shape by vacuum deposition without using a mask. The manufacturing method of the said photoelectric conversion apparatus.

  In the solar cell of the present invention, reliability and conversion efficiency can be improved by improving the adhesion strength and short-circuit current of the back surface metal electrode layer.

It is the figure which showed typically the cross section of the photoelectric conversion apparatus of this invention. It is a figure which shows the reflective characteristic of a back surface metal electrode / low refractive index material layer / back surface metal electrode layer structure. It is the figure which showed typically the structure of the low refractive index material vicinity of the photoelectric conversion apparatus of this invention. It is a figure which shows the measurement result of the electrostatic capacitance of the photoelectric conversion apparatus of this invention. It is a figure which shows the transmission electron microscope image of the low refractive index material vicinity of the photoelectric conversion apparatus of this invention.

  The photoelectric conversion device of the present invention is “a photoelectric conversion device having at least a photoelectric conversion unit, a back transparent conductive layer, an island-shaped low refractive index material, and a back metal electrode layer in this order, wherein the low refractive index The material has a thickness of 1 nm to 10 nm ".

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In each drawing of the present application, dimensional relationships such as thickness and length are appropriately changed for clarity and simplification of the drawings, and do not represent actual dimensional relationships. Moreover, in each figure, the same referential mark represents the same part or an equivalent part.

  FIG. 1 is a schematic cross-sectional view of a multi-junction silicon-based photoelectric conversion device according to an example of an embodiment of the present invention. On the translucent insulating substrate 1, a light incident side transparent conductive layer 2, a front photoelectric conversion unit 3, a rear photoelectric conversion unit 4, a back transparent conductive layer 5, a low refractive index material 6 (not shown in FIG. 1), The back surface metal electrode layers 7 are arranged in this order. The back transparent conductive layer and the back metal electrode layer are collectively referred to as a back electrode. Each of the front photoelectric conversion unit and the rear photoelectric conversion unit includes a p-type silicon thin film layer, an i-type silicon thin film layer, and an n-type silicon thin film layer.

  In FIG. 1, the photoelectric conversion unit is a two-junction photoelectric conversion device that includes a front photoelectric conversion unit and a rear photoelectric conversion unit. In the present invention, three or more photoelectric conversion units are stacked. It can also be applied to a multi-junction silicon-based photoelectric conversion device. Examples of the three-junction silicon photoelectric conversion device include an amorphous silicon photoelectric conversion unit as the first photoelectric conversion unit, an amorphous silicon germanium or crystalline silicon photoelectric conversion unit as the second photoelectric conversion unit, and a third photoelectric conversion unit. A case where an amorphous silicon germanium or a crystalline silicon-based photoelectric conversion unit is applied to the unit is mentioned, but the combination of the photoelectric conversion units is not limited to this. Here, it shall be laminated | stacked on the light-incidence side transparent conductive layer in order of the 1st to 3rd photoelectric conversion unit.

A plate-like member or a sheet-like member made of glass, transparent resin, or the like can be applied to the translucent insulating substrate 1 used in a photoelectric conversion device of a type in which light enters from the substrate side. The upper transparent conductive layer 2 is preferably made of a conductive metal oxide such as SnO ₂ (tin oxide) or ZnO (zinc oxide), and is formed using a method such as CVD (chemical vapor deposition), sputtering, or vapor deposition. It is preferable. The upper transparent conductive layer 2 is desirably provided with a function of scattering incident light by providing a fine uneven structure (texture structure) on the surface thereof. In addition, it is desirable to add a dopant such as fluorine, antimony, boron, aluminum, gallium, silicon, or hydrogen to the conductive metal oxide.

  At least one photoelectric conversion unit is disposed behind the light incident side transparent conductive layer 2. In the case of a structure in which two photoelectric conversion units are stacked as shown in FIG. 1, the front photoelectric conversion unit 3 disposed on the light incident side has a relatively wide bandgap material, for example, an amorphous silicon-based material. A conversion unit or the like is preferably used. The rear photoelectric conversion unit 4 arranged on the rear side includes a material having a relatively narrow band gap, for example, a photoelectric conversion unit made of a silicon-based material containing crystalline material, an amorphous silicon germanium photoelectric conversion unit, or the like. Preferably used.

  Each photoelectric conversion unit is preferably constituted by a pin junction including a p-type layer, an i-type layer that is a substantially intrinsic photoelectric conversion layer, and an n-type layer. 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 the amorphous or crystalline silicon-based material is 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, and germanium. Good.

  Further, the main constituent material of the conductive type layer is not necessarily the same as that of the i-type layer. For example, amorphous silicon carbide or the like can be used for the p-type layer of the amorphous silicon photoelectric conversion unit. A silicon layer containing crystal in the n-type layer (also referred to as μc-Si) or the like can be used.

  Next to the rear photoelectric conversion unit 4, a back transparent conductive layer 5 is formed. The back transparent conductive layer 5 desirably has excellent denseness and has a function of preventing the metal material of the back metal electrode layer 7 from diffusing and mixing into the crystalline silicon photoelectric conversion unit 4. Moreover, it is desirable to adjust the film thickness etc. of the back surface transparent conductive layer 5 so that an optimal reflection characteristic can be provided in the optical reflection in a back surface electrode.

The back transparent conductive layer 5 can be made of an oxide such as ZnO, ITO (indium tin oxide), SnO ₂ , etc. Among them, ZnO is preferably used. This is because ZnO is inexpensive because it contains abundant materials, has high transmittance, and is excellent as a diffusion preventing layer. As the above oxide, an intrinsic oxide to which no impurity is added can be used, but a doped one is also preferably used. For example, when ZnO is used, it is desirable that aluminum, gallium, boron or the like be doped in order to reduce the resistivity.

  The method for forming the back transparent conductive layer 5 is not particularly limited as long as it is a means for forming a uniform thin film. For example, in addition to PVD (Physical Vapor Deposition) methods such as sputtering and vacuum deposition, and various CVD (Chemical Vapor Deposition) methods, a solution containing a transparent electrode layer raw material is spin-coated or roll-coated. And a method of forming a transparent electrode layer by heat treatment after coating by spray coating or dipping coating.

  The film thickness of the back transparent conductive layer 5 is preferably 5 nm or more and 500 nm or less, and more preferably 15 nm or more and 90 nm or less. If the film thickness of the back surface transparent conductive layer 5 is within the above range, the loss due to light absorption in the back surface transparent conductive layer can be almost ignored, and diffusion / mixing of the metal material of the back surface metal electrode layer into the conversion unit can be prevented. It is because the effect which prevents is also acquired.

  After the back transparent conductive layer 5 formed in this way, a back metal electrode layer 7 material is formed. As the back metal electrode layer material, Ag can be preferably used. This is because Ag has a high reflectance and a high conductivity in the near ultraviolet to infrared region. The back metal electrode layer material can be formed by a method such as sputtering or vapor deposition.

  A low refractive index material is formed between the back transparent conductive layer 5 and the back metal electrode layer 7.

Here, the low refractive index material is a material having a refractive index lower than that of the back transparent conductive layer material in a wavelength range in which the photoelectric conversion unit has sensitivity.

Specific examples of the low refractive index material include group I elements (Na, Li, etc.), group II elements (Mg, Ca, Sr, Ba, Zn, etc.), group III elements (B, Al, etc.), and group IV. Fluorides such as elements (Si, etc.) and rare earth elements (La, Ce), oxides, oxyfluorides, nitrides, oxynitrides, etc. are known. Of these, fluorides are desirable, and examples of desirable materials Examples thereof include LiF and MgF ₂ .

  This is because when the above-described materials are used as the low refractive index material in the present invention, an island-shaped low refractive index material can be easily formed on the back transparent conductive layer.

  The thickness of the low refractive index material is 1 nm or more and 10 nm or less. By setting it as the thickness of this range, 30 to 90% area | region of a back surface transparent conductive layer surface can be coat | covered with a low refractive index material, and the reliability and conversion efficiency of a photoelectric conversion apparatus can be improved. In particular, when the thickness is 2 nm or more and 5 nm or less, a particularly large enhancement effect is obtained with respect to the adhesion strength between the back transparent conductive layer and the back metal electrode layer, and even if the low refractive index material itself absorbs light, It is more preferable because the influence can be sufficiently reduced and a high reflectance improvement effect can be expected.

  As the low refractive index material, it is preferable to use a material containing LiF and having a thickness of 1 nm to 10 nm. By using the above, it is possible to easily form an island-shaped low refractive index material. At this time, a thickness of 2 nm or more and 5 nm or less can be used more preferably, and a thickness of 4 nm or more and 5 nm or less can be used particularly preferably.

The low refractive index material preferably contains MgF ₂ and has a thickness of 1 nm or more and less than 5 nm. By using the above, it is possible to easily form an island-shaped low refractive index material.

A second transparent layer (low refractive index layer) having a refractive index lower than that of the first transparent layer is sandwiched between the metal layer (back metal electrode layer) and the first transparent layer (back transparent conductive layer). The technique for improving the reflectance with the so-called “increased reflection mirror” is a known technique. As an example, in a simple three-layer structure of Ag (film thickness: 300 nm) / LiF / ZnO (film thickness: 80 nm), the reflection spectrum when light is incident from the ZnO side using the LiF film thickness as a parameter is non-patent document. The results calculated by the method described in 1 are shown in FIG.
J. et al. Krc et al. , Progress in Photovoltaics 11 (2003) 15.

  In order to clearly improve the reflectance at a wavelength of 700 to 1000 nm that can contribute the most improvement in characteristics in a multi-junction silicon photoelectric conversion device in which an amorphous silicon photoelectric conversion unit and a crystalline silicon photoelectric conversion unit are laminated from FIG. It can be confirmed that the thickness of the low refractive index material (LiF) needs to be at least 20 nm or more, preferably 40 nm or more. On the other hand, since a low refractive index material is generally electrically insulating, as pointed out in Patent Document 1 and Special Document 2, it is thick between the back metal electrode layer and the back transparent conductive layer. If the low refractive index material layer is sandwiched, the electrical connection between the back metal electrode layer and the back transparent conductive layer deteriorates and the solar cell characteristics deteriorate, so the thickness of the low refractive index material should be increased. I can't. In such a mechanism, in Patent Document 2, the solar cell characteristics such as the conversion efficiency are improved as the film thickness of the low refractive index layer is increased, and the maximum is obtained at 20 nm, and the conversion efficiency is lowered when the thickness exceeds 20 nm. This is considered to correspond to this. In view of such problems, the light absorption at the low refractive index material / back metal electrode layer interface was examined in detail, and a new idea for the shape of the low refractive index material was obtained.

That is, light absorption at the low refractive index material / back surface metal electrode layer interface is mainly caused by surface plasmon polaritons (hereinafter referred to as surface plasmons) when light is irradiated onto the low refractive index material / back surface metal electrode layer interface. This occurs by attenuating near the low refractive index material / back metal electrode layer interface. When the low refractive index material is formed in an island shape and the width is sufficiently smaller than the attenuation distance of the surface plasmon (the distance at which the intensity becomes 1 / e), the surface generated at the low refractive index material / back metal electrode layer interface Since the plasmon reaches the interface with the back transparent conductive layer before the surface plasmon disappears, the surface plasmon generated between the low refractive index material / back surface metal electrode layer when the low refractive index material is formed in a layer form is: It will have different characteristics and as a result the reflectivity may change. Further, the attenuation distance of the surface plasmon low refractive index material / back surface metal electrode layer interface direction (width direction of the island-shaped low refractive index material) is described in Non-Patent Document 2 in the case of the interface between the layered LiF and Ag. It can be expected that the width of the island-shaped low refractive index material should be 50 μm or less.
Journal of Plasma and Fusion Research 84 (2008) 10.

  Accordingly, the present inventors have conducted intensive studies on a multi-junction silicon photoelectric conversion device formed with particular attention so that the shape of the low refractive index material is not a layer but an island shape. It has been found that when the shape is made in an island shape, a remarkable effect of improving the reflectance can be obtained even when the thickness of the low refractive index material is as thin as 2.5 nm or less. Further surprisingly, it has been clarified that the adhesion strength of the back metal electrode layer can be greatly increased.

  Here, one form of the low refractive index material formed on the surface of the back transparent conductive layer will be described with reference to FIG. FIG. 3 schematically shows the cross-sectional shapes of the rear photoelectric conversion unit 4, the back surface transparent conductive layer 5, the low refractive index material 6, and the back surface metal electrode layer 7. The surface of the rear photoelectric conversion unit has two structures, a concavo-convex structure formed naturally during film formation of the rear photoelectric conversion unit and a concavo-convex structure based on the surface concavo-convex structure of the light incident side transparent conductive layer which is the base of the photoelectric conversion unit The concavo-convex structure is superimposed. Since the film thickness of the back surface transparent conductive layer is smaller than the height difference of the concavo-convex structure of the rear photoelectric conversion unit, the surface shape of the back surface transparent conductive layer is generally in the shape of the surface shape of the rear photoelectric conversion unit. The distance between adjacent concave and convex portions is about 0.1 to 10 μm, and the height difference (H1) is about 0.1 to 0.3 μm.

  In order to form the concavo-convex structure on the back surface transparent conductive layer surface, the back surface transparent conductive layer itself may be provided with a concavo-convex structure, but the concavo-convex structure is formed on the surface of the back surface transparent conductive layer, that is, the surface of the photoelectric conversion unit. In addition, a concavo-convex structure can be easily produced by forming a backside transparent conductive layer along this shape. In order to form a concavo-convex structure on the surface of the photoelectric conversion unit, the concavo-convex structure may be provided on the substrate, the light incident side transparent conductive layer, or the photoelectric conversion unit itself.

  In the present invention, the term “island” is a three-dimensional island-like growth (Volmer-Weber type), which is commonly used in the field of thin film formation technology, as seen in the initial stage of thin film crystal growth. ) Or a structure formed by oblique vapor deposition on an uneven structure as will be described later, and the low refractive index material is not formed over the entire surface of the back surface transparent conductive layer, but the back surface transparent conductive layer surface. The state which has the non-formation part of a low-refractive-index material in part.

  As a method for forming a low refractive index material, a liquid phase method such as a sol-gel method can be used. However, a film forming method using a gas phase method, for example, a sputtering method or a vacuum evaporation method is more reproducible. This is suitable because it is easy to form a low refractive index material. Note that when the film is formed by using the vapor phase method, the substrate temperature is preferably as low as about room temperature, and more preferably cooled to room temperature or lower. This is because diffusion due to migration of the low refractive index material flying from the evaporation source on the back surface transparent conductive layer surface can be suppressed. For the same reason, even when the vapor phase method is used, the vacuum deposition method is more preferable than the sputtering method.

  In addition, when the surface of the back transparent conductive layer has a concavo-convex structure as described above, an island-shaped low refractive index material can be formed with higher reproducibility by using a vacuum deposition apparatus and using an oblique deposition method. Can do. This is because, in the oblique vapor deposition method, the convex portion of the concavo-convex structure becomes a shadow, and the vapor deposition material does not easily adhere to the concave portion.

  As for the surface of a back surface transparent conductive layer, it is desirable that the part of 30% or more and 90% or less is covered with a low refractive index material. Within this range, the effect of increasing reflection by inserting a low refractive index material and the effect of enhancing the adhesion of the back metal electrode layer can be obtained, and further, between the back metal electrode layer and the back metal electrode layer. Also good electrical connection can be realized.

  In the low refractive index layer in the present invention, the width of the low refractive index layer forming portion is preferably 0.01 to 50 μm, and the width of the non-forming portion is preferably 0.001 to 10 μm. Of these, 0.1 to 10 μm and 0.03 to 3 μm are more preferable, respectively. By being in the said range, the favorable electrical connection between a back surface metal electrode layer and a back surface metal electrode layer and the high reflectance improvement effect can be anticipated.

In order to simply form an island-shaped low refractive index material, mask vapor deposition may be used as described in Patent Document 1, but the size (width) of the low refractive index material forming portion is 50 μm or less. In order to form a low refractive index material so that the coverage is in the range of 30 to 90%, in consideration of the flatness of the mask and the seepage from the opening during vapor deposition, Special attention is required.

  The formation of the low refractive index material in an island shape may be confirmed by observing the cross-sectional structure using, for example, a transmission electron microscope. The magnification is about 100,000 to 1,000,000 times, and the formation state of the low refractive index material can be confirmed by observing a cross section including between the back transparent conductive layer and the back metal electrode layer.

  In general, in observation with a transmission electron microscope, the visual field to be observed is likely to be a very small region compared to the area of the solar battery cell. For this reason, the case where the actual condition of the whole photovoltaic cell and the observation result by a transmission electron microscope do not necessarily correspond may arise. Therefore, in order to confirm the validity of the observation result by the transmission electron microscope, it is desirable to perform a macro evaluation different from the microscopic observation by the transmission electron microscope.

Specifically, the method of measuring the electrostatic capacitance of a photovoltaic cell in a dark box is mentioned. In general, a photoelectric conversion unit can be regarded as an insulator under a low voltage because a current does not flow even if a voltage is applied if it is a low voltage of about several to several tens of mV without light irradiation. In addition, if the resistance is sufficiently higher than that of the back transparent conductive layer (for example, 3 digits or more), the low refractive index material can be substantially regarded as an insulator. For this reason, when a low refractive index material is formed in layers, the equivalent circuit of the photoelectric conversion device shall be described with a structure in which a capacitor corresponding to the photoelectric conversion unit and a capacitor corresponding to the low refractive index material layer are connected in series. Can do. Therefore, when the dielectric constant and thickness of the photoelectric conversion 換Yu knit is constant, so that the monotonically capacitance with increasing thickness of the low refractive index material decreases. On the other hand, when the low refractive index material is formed in an island shape, a portion where the back transparent conductive layer and the back metal electrode layer are in direct contact with each other occurs. The volume resistivity of the back metal electrode layer ^{(10-2 6} [Omega] cm order) is generally from extremely lower than back transparent conductive layer (at most 10 ^{@ 4} [Omega] cm order) and low refractive index material, the low was formed in an island shape Even if the dimension of the refractive index material is, for example, about 10 μm, the back surface metal electrode layer and the back surface transparent conductive layer have almost the same potential on one side, and therefore no potential difference (electric field) can occur in the low refractive index material portion. Therefore, the influence of the low refractive index material portion formed in an island shape can be electrically ignored, and the capacitance does not change even when the low refractive index material formed in an island shape is provided.

The relationship between the structure of the low refractive index material and the capacitance described above will be described in more detail by giving a specific example. First, in an amorphous silicon single-junction solar cell in which LiF is introduced as a low refractive index material between the back transparent conductive layer and the back metal electrode layer, the relationship between the LiF deposition time and the solar cell capacitance evaluated. In this evaluation, a vacuum deposition method was used for LiF film formation, and a film formation rate of 0.01 ± 0.001 nm / min was used under a vacuum of the order of 10 ⁻⁵ Pa using a crystal oscillator type film thickness meter. Film formation was performed using a crucible whose temperature was adjusted so as to be 2 seconds as a deposition source. In addition, the substrate was not particularly heated during LiF film formation. Prior to this examination, a LiF thin film having a thickness of about 100 nm was formed, and the film thickness was measured with a stylus type step gauge to calibrate the quartz vibrator type film thickness meter. After the LiF film was formed, Ag was continuously formed to a thickness of 250 nm, a terminal was provided between the Ag layer and the light incident side transparent conductive layer, and the capacitance was measured. An LCR meter was used for measurement, and the frequency (f) at the time of measurement was 100 Hz, and the alternating voltage (V _PP ) was 50 mV.

  For comparison, an amorphous silicon single-junction solar cell in which LiF was formed by sputtering was fabricated, and the capacitance was measured. The reason why the sputtering method is used here is that the sputtering method is more likely to be a layered film than the vacuum deposition method. Note that the input power was adjusted in advance so that the deposition rate was 0.01 nm / second even when LiF was deposited by sputtering.

  The measurement results are shown in FIG. As described above, assuming that LiF is formed in layers from the initial stage of film formation, the capacitance of the amorphous silicon single-junction solar cell is expected to decrease as the film formation time increases. In the amorphous silicon single-junction solar cell in which the LiF film was formed by the sputtering method, the result was in agreement with this expectation, but the amorphous silicon single-junction solar cell formed by using the vacuum evaporation method The measurement results did not correspond to this, and almost no decrease in capacitance was observed until the film formation time was approximately 800 seconds. On the other hand, when the film forming time exceeded about 800 seconds, the capacitance was reduced. From the above consideration, this phenomenon can be interpreted that LiF is first formed in an island shape, and then the LiF formed in an island shape grows larger to come into contact with adjacent LiF, and the shape changes into a layer shape. Therefore, when the film formation time is 800 seconds or less, the shape of LiF is an island shape, and when it exceeds 800 seconds, it can be determined from the capacitance measurement that it is a layer shape.

If an excessive current flows during capacitance measurement and it is difficult to measure the capacitance, the current may be suppressed by applying a bias voltage in the reverse direction. Also, if the cell area is large and evaluation is difficult due to voltage drop due to the resistance of the metal electrode or the light-incident side transparent conductive layer, the cell is divided into sizes that are easy to evaluate using a laser scribing method, for example, about 1 cm ^2. And evaluate it.

  As described above, the shape of the low refractive index material can be specifically evaluated by using the observation of the shape with a transmission electron microscope and the capacitance measurement in combination.

  In addition, although embodiment was demonstrated using the silicon system thin film solar cell, this is not limited to a silicon system thin film solar cell, it has a back surface metal electrode layer and a back surface transparent electrode, and injects into a back surface electrode A similar effect can be obtained if the solar cell is configured to reach light.

  The photoelectric conversion device according to the present invention is a multijunction solar cell, particularly a multijunction thin film solar cell in which an amorphous silicon photoelectric conversion unit is disposed on the light incident side and a crystalline silicon photoelectric conversion unit is disposed on the back electrode side. It can be preferably used. In the case of a solar cell having this configuration, since the light absorption coefficient of the power generation layer of the crystalline silicon-based photoelectric conversion unit is not large, sunlight incident on the solar cell has a plurality of gaps between the back electrode and the light incident side transparent electrode. There will be round trips. One method for realizing high characteristics in the solar cell is to sufficiently absorb incident light with a crystalline silicon-based photoelectric conversion unit. To achieve this, the film thickness of the power generation layer may be increased. However, this method is uneconomical because the time required for film formation becomes long, leading to a decrease in open-circuit voltage, and further, There is a tendency that the silicon photoelectric conversion unit is easily peeled off. On the other hand, according to the method for improving the reflectance of the back electrode disclosed in the present invention, it is expected to improve the solar cell characteristics without causing these problems.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example.

(Examples 1-3)
The photoelectric conversion device having the structure shown in FIG. 1 was manufactured by the following method . The translucent insulating substrate 1, using non-alkali glass substrate. The light incident side transparent conductive layer 2 was made of SnO ₂ produced by a thermal CVD method. At this time, the film thickness of the transparent conductive layer 2 was 800 nm, the sheet resistance was 10Ω / □, and the haze was 15 to 20%.

  On this, a boron-doped p-type silicon carbide (SiC) layer is 10 nm, a non-doped amorphous silicon photoelectric conversion layer is 250 nm, and a phosphorus-doped n-type μc-Si layer is 20 nm thick using a high-frequency plasma CVD apparatus. To form a film. As a result, a pin junction amorphous silicon photoelectric conversion unit (front photoelectric conversion unit) 3 as a front photoelectric conversion unit was formed.

  Further, a boron-doped p-type microcrystalline silicon layer was formed by plasma CVD with a thickness of 15 nm, a non-doped crystalline silicon photoelectric conversion layer with a thickness of 700 nm, and a phosphorus-doped n-type microcrystalline silicon layer with a thickness of 20 nm. Thus, a pin junction crystalline silicon photoelectric conversion unit (rear photoelectric conversion unit) 4 as a rear photoelectric conversion unit was formed.

  After the crystalline silicon photoelectric conversion unit formed process work in process is taken out from the high frequency plasma CVD apparatus into the atmosphere, it is introduced into the film forming chamber of the high frequency magnetron sputtering apparatus, and on the rear photoelectric conversion unit 4 as a back transparent conductive layer A ZnO (AZO) layer to which Al having a thickness of 80 nm was added was formed.

  Here, a ZnO sintered body added with 2 wt% Al was used as a sputtering target. Ar gas was introduced as a sputtering gas, the substrate was heated to 150 ° C., the pressure was set to 0.27 Pa, and an AZO layer was formed. After the AZO layer was formed, the work piece in process on which the back surface transparent conductive layer had been formed was taken out from the high-frequency magnetron sputtering apparatus into the atmosphere, and then introduced into a vacuum vapor deposition machine to deposit a low refractive index material.

Here, LiF powder (manufactured by High Purity Chemical, purity: 99.9% or more) was used as the vapor deposition material. During film formation, the crucible containing LiF powder was heated to about 700 ° C. to evaporate (sublimate) LiF. The degree of vacuum during film ^formation was 1 × 10 ⁻⁴ Pa or less, and the film formation rate was 0.01 ± 0.001 nm / second. The amount of low refractive index material formed was controlled by changing the film forming time. The film forming speed during film formation was observed with a crystal oscillator type film thickness meter, and the film forming speed was kept within a certain range by controlling the crucible temperature.

Subsequently, an Ag layer having a film thickness of 250 nm was formed as a back metal electrode layer using a vacuum deposition apparatus. The degree of vacuum during film ^formation was 1 × 10 ⁻⁴ Pa or less, and the film formation rate was 0.2 ± 0.02 nm / second.

  In addition, three types of multi-junction silicon solar cells having a low refractive index material deposition time of 250 seconds (Example 1), 500 seconds (Example 2), and 750 seconds (Example 3) were manufactured. Prior to this experiment, the film was formed on a single crystal silicon substrate for 100 minutes to calibrate the quartz crystal thickness meter, and the refractive index of the LiF layer formed on the single crystal silicon substrate was determined by spectroscopic ellipsometry. It was measured by a measurement method. The refractive index of the LiF layer at a wavelength of 600 nm was 1.38. Similarly, when the refractive index of AZO was measured, it was 1.91, and it was confirmed that LiF had a lower refractive index than AZO.

(Comparative Example 1)
It was produced in the same manner as in Example 1 except that the low refractive index material forming step was not included.

(Comparative Example 2)
It was fabricated in the same manner as in Example 1 except that the LiF film formation time was 1100 seconds.

(Comparative Examples 3-5)
It was fabricated in the same manner as in Example 1 except that the LiF formation method was a high frequency magnetron sputtering method. That is, LiF film formation uses a 100 mmφ LiF target (manufactured by High-Purity Chemical, purity 99.9%), and under an Ar atmosphere, the pressure is 8 Pa, the high-frequency power is 300 W, the substrate temperature is 150 ° C. The times were 400 seconds (Comparative Example 3), 800 seconds (Comparative Example 4), and 1200 seconds (Comparative Example 5), respectively. The film formation speed at this time was 0.01 nm / second.

(Comparative Example 6)
It was fabricated in the same manner as in Example 2 except that MgF ₂ was used as the low refractive index material and the electron beam evaporation method was used as the film forming method. The refractive index of MgF ₂ was 1.39. Note that the MgF ₂ film forming method was based on the method described in Patent Document 2.

The photoelectric conversion characteristics of the photoelectric conversion devices of the above-described examples and comparative examples are obtained by using a solar simulator having a spectrum distribution of AM1.5 and using simulated solar light at an energy density of 100 mW / cm ² at 25 ° C. The output characteristics were measured by irradiating and the open circuit voltage (Voc), short circuit current density (Jsc), fill factor (FF), and power generation efficiency (Eff) were obtained. The adhesion strength of the back metal electrode layer was determined by a tape peeling test. In the tape peeling test, a test tape (550P, Sumitomo 3M) was attached on the back surface metal electrode layer, and was peeled off at a stretch from the surface of the back surface metal electrode layer in the vertical direction. The adhesion strength was determined by measuring the adhesion rate of the back metal electrode layer to the peeled tape adhesive surface. 1. Adhesion rate of 80% or more 2. Adhesion rate 60% or more and less than 80% 3. Adhesion rate of 40% or more and less than 60% Evaluation was made by classifying into five stages of adhesion rate of 20% or more and less than 40% or less than 5.20%. Further, the shape of the low refractive index material was observed using a transmission electron microscope (HF2000 manufactured by Hitachi, Ltd.), and the ratio (coverage) at which the back transparent conductive layer was covered with the low refractive index material was measured. Here, the coverage is the length (A) of the surface of the backside transparent conductive layer on the backside metal electrode layer side from the transmission electron microscope image, and the length of the portion where the backside transparent conductive layer and the low refractive index material are in contact with each other. (B) was read and calculated by (B) / (A).

  First, as an example of this evaluation, FIG. 5 shows a transmission electron microscope image in the vicinity of the interface between the back transparent conductive layer and the back metal electrode layer of the multijunction solar cell of Example 2. In FIG. 5, a portion where LiF is formed is surrounded by a dotted line. From the cross-sectional image shown in FIG. 5, it can be confirmed that LiF is formed only on a part of the back transparent conductive layer, that is, formed in an island shape. Moreover, when the coverage was measured regarding this sample, the coverage was 60%. Moreover, the thickness of LiF read from the transmission electron microscope image was 5 ± 1 nm, which almost coincided with the product of the film formation speed and the film formation time.

Table 1 below shows the coverage of the multi-junction silicon solar cell, the adhesion strength of the back surface metal electrode layer, the capacitance (relative value to Comparative Example 1), and the photoelectric conversion characteristics. The characteristics of the multi-junction silicon solar cells given as examples and comparative examples are shown in a ratio with the characteristics of the conventional multi-junction silicon solar battery mentioned as comparative example 1. The solar cell characteristics of Comparative Example 1 are as follows. The open circuit voltage is 1.38 V, the short circuit current density is 8.5 mA / cm ² , the fill factor is 83%, the power generation efficiency is 9.7%, and the capacitance is 61 nF. Met.

The thickness shown in Table 1 is a value calculated from the product of the film forming speed and the film forming time.

  From the results in Table 1, first, regarding the adhesion strength of the back surface metal electrode layer, even if a layered low-refractive index material is inserted between the back surface transparent conductive layer and the back surface metal electrode layer, no improvement in adhesion force can be obtained. However, it can be read that the adhesion strength of the back surface metal electrode layer is increased by inserting the island-shaped low refractive index material. In addition, it can be seen that in order to obtain a high adhesion strength of the back metal electrode layer, it is desirable to set the coverage of the low refractive index material within the range of 30 to 90%.

  On the other hand, with respect to the solar cell characteristics, it is recognized that the short circuit current and the fill factor tend to increase as the coverage increases up to 60%. When the coverage exceeds 60%, the short-circuit current increases until the coverage is 90%, and then tends to saturate. Therefore, it is considered that a low refractive index material having a coverage of about 60%, that is, a thickness of about 5 nm is particularly preferable. On the other hand, the curve factor decreases at 60% as a boundary, but if it is within the range of 30 to 90%, a photoelectric conversion device that is more efficient than the photoelectric conversion device that does not include the low refractive index material of Comparative Example 1 is realized. can do.

  The electrostatic capacity of the photoelectric conversion device of Comparative Example 3 was 59.6 nF. This value is lower than the capacitance 61 nF of the photoelectric conversion device of Comparative Example 1. Since the electrostatic capacity is thus reduced, it can be confirmed that when LiF is formed by sputtering, the shape of LiF is layered unlike the vacuum deposition method. Moreover, even if the thickness of a low refractive index material is equivalent from the comparison of Examples 1-3 and Comparative Examples 3-5, the direction which made the shape of the low refractive index material into island shape adheres a back surface metal electrode layer. It can be seen that both the strength and the conversion efficiency are increased.

From the result of Comparative Example 6, when MgF ₂ having a film thickness of 5 nm is used as the low refractive index material, the capacitance is lower than that of Comparative Example 1, so that the shape of the low refractive index material is island-shaped. Therefore, it can be seen that the FF decreases due to the deterioration of the electrical connection between the back surface transparent conductive layer and the back surface metal electrode layer, and the adhesion strength of the back surface metal electrode decreases. Also from this result, it can be confirmed that the low refractive index layer described in Patent Document 2 is layered.

  From the above results, it is considered that by using an island-shaped low refractive index material, a photoelectric conversion device having high adhesion strength with the back surface metal electrode layer and high conversion efficiency can be obtained.

DESCRIPTION OF SYMBOLS 1 Translucent insulated substrate 2 Light incident side transparent conductive layer 3 Front photoelectric conversion unit 4 Back photoelectric conversion unit 5 Back surface transparent conductive layer 6 Low refractive index material 7 Back surface metal electrode layer

Claims (7)

At least a photoelectric conversion unit, a back surface transparent conductive layer, an island-like low refractive index material having a refractive index lower than that of the back surface transparent conductive layer in a wavelength region where the photoelectric conversion unit is sensitive, and a back metal electrode layer A photoelectric conversion device in order,
The low refractive index material and the back metal layer are in direct contact,
The low refractive index material, a photoelectric conversion device according to claim Rukoto thickness Ri der than 10nm or less 1 nm, is formed on the width-like island 0.01Myuemu～50myuemu.   The photoelectric conversion device according to claim 1, wherein the low refractive index material includes LiF. _{2. The} photoelectric conversion device according to claim 1, wherein the low refractive index material includes MgF ₂ and has a thickness of 1 nm or more and less than 5 nm.   4. The photoelectric conversion device according to claim 1, wherein a portion of 30% or more and 90% or less of the surface of the back transparent conductive layer is covered with the low refractive index material. The said back surface transparent conductive layer is comprised from the oxide which contains at least one in In, Zn, Al, Ga, and B in a structural element, The any one of Claims 1-4 characterized by the above-mentioned. Photoelectric conversion device. A method for producing the photoelectric conversion device according to any one of claims 1 to 5 ,
The back transparent conductive layer has a concavo-convex structure on the surface on the low refractive index material forming side,
A method for manufacturing a photoelectric conversion device, wherein the low refractive index material is formed into an island shape by a vacuum deposition method without using a mask. The method for producing a photoelectric conversion device according to claim 6 , wherein the low refractive index material is formed by an oblique vapor deposition method.