BUFFER LAYER FILM-FORMING METHOD AND BUFFER LAYER

Abstract

The present invention relates to a method for film-forming a buffer layer to be used for a solar cell, the buffer layer being disposed between a light absorbing layer and a transparent conductive film. Specifically, in this buffer layer film-forming method, a solution (4) is formed into a mist, the solution containing zinc and aluminum as metal raw materials of the buffer layer. Then, a substrate (2) disposed in the atmosphere is heated. Then, the mist of the solution is sprayed to the substrate being heated.

Claims

1. A method for film-forming a buffer layer to be used for a solar cell, the buffer layer being disposed between a light absorbing layer and a transparent conductive film comprising the steps of: (A) forming a solution (4) containing zinc and aluminum as metal raw materials of the buffer layer into a mist, (B) heating a substrate (2) disposed in the atmosphere, and (C) spraying a mist of said solution atomized in said step (A) to said substrate in said step (B).

2. The method for film-forming a buffer layer according to claim 1 further comprising the step of: (D) supplying ozone to said substrate in said step (B).

3. The method for film-forming a buffer layer according to claim 1, wherein said solution contains ammonia.

4. The method for film-forming a buffer layer according to claim 1, wherein said solution contains a metal compound having zinc and aluminum, and said metal compound is a -diketone compound.

5. A buffer layer to be used for a solar cell, the buffer layer being disposed between a light absorbing layer and a transparent conductive film, wherein said buffer layer is a Zn.sub.1-xAl.sub.xO film containing zinc and aluminum, provided that 0<x<1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0020] FIG. 1 is a view showing a configuration of a film forming apparatus in which a method for film-forming a buffer layer according to the present invention is implemented.

[0021] FIG. 2 is a view showing another configuration of a film forming apparatus in which a method for film-forming a buffer layer according to the present invention is implemented.

[0022] FIG. 3 is a view showing the results of band gap measurement performed on a film-formed buffer layer.

[0023] FIG. 4 is a view showing the results of resistivity measurement performed on a film-formed buffer layer.

[0024] FIG. 5 is a view showing a ratio of aluminum contained as a mixed crystal in a buffer layer produced using a solution containing zinc and aluminum.

[0025] FIG. 6 is a view showing a band gap and resistivity in a film produced using a solution containing zinc and magnesium.

[0026] FIG. 7 is a view showing the results of transmittance measurement performed on a film-formed buffer layer.

DESCRIPTION OF EMBODIMENTS

[0027] The present invention relates to a buffer layer to be used for a solar cell, the buffer layer being disposed between a light absorbing layer and a transparent conductive film, and a method for film-forming the buffer layer. The present inventors found through a great deal of research and development that a Zn.sub.1-xAl.sub.xO film containing zinc and aluminum is useful as a novel buffer layer. Here, x satisfies a relationship of 0<x<1. Further, the present inventors also found that as the method for film-forming a buffer layer, a mist method implemented in the atmosphere, described later, is useful.

[0028] In addition, as described above, an object of the present invention is a buffer layer, and is not a conductive film which is low in resistance. Here, a trace of aluminum is sometimes introduced into a zinc oxide film as a dopant. This film (Al-doped ZnO) is a conductive body (resistivity is about 10.sup.3 .Math.cm or less), and the amount of aluminum introduced thereinto is at most about 1% with respect to the amount of zinc. Further, when aluminum is introduced into the zinc oxide film as a dopant, transmittance tends to be reduced in the film to be film-formed (particularly, the transmittance of light of a wavelength of 1500 nm or longer tends to be significantly reduced).

[0029] In contrast with this, the buffer layer of the object of the present invention is a Zn.sub.1-xAl.sub.xO film (0<x<1), and even when the amount of aluminum to be mixed is changed, high transparency is maintained (for example, a high value is maintained even in the transmittance of light of a wavelength of 1500 nm or longer in the Zn.sub.1-xAl.sub.xO film according to the present invention).

[0030] Further, in the present invention, aluminum to be mixed is employed as metal raw materials of the buffer layer to be produced (that is, aluminum is contained as a mixed crystal in the film film-formed). Accordingly, the Zn.sub.1-xAl.sub.xO film according to the present invention includes aluminum in an amount larger than the amount in the case where aluminum is introduced as a dopant. In the present invention, an amount of aluminum relative to an amount of zinc in a raw material solution is, for example, 10% or more. Further, the resistivity of the Zn.sub.1-xAl.sub.xO film is 10 .Math.cm or more, and the film is not said to be a conductor.

[0031] A Zn.sub.1-xAl.sub.xO film serving as the buffer layer is produced by using zinc and aluminum which are easily handled and disposed of and is inexpensive. Therefore, production of the buffer layer becomes easy and production cost can be reduced. Further, the present inventors found that in the buffer layer, the band gap and the resistivity of the buffer layer can be controlled (adjusted) over a wide range by varying an amount of aluminum relative to an amount of zinc.

[0032] Hereinafter, in embodiments, the method for film-forming a buffer layer will be specifically described based on drawings.

Embodiments

[0033] FIG. 1 is a view showing a schematic configuration of an apparatus for film-forming a buffer layer of the present embodiment.

[0034] As shown in FIG. 1, the apparatus for film-forming a buffer layer 100 of Embodiment 1 is configured of a reaction container 1, a heater 3, a solution container 5 and a mist generator 6.

[0035] In the film forming apparatus 100, the mist method is implemented. That is, by spraying a mist of raw material solution 4 to the substrate 2 disposed in the atmosphere, a buffer layer is film-formed on the substrate 2.

[0036] Here, the heater 3 is disposed in the reaction container 1. Then, the substrate 2 is heated by the heater 3 during film-forming. Further, a light absorbing layer is film-formed on the surface of the substrate 2.

[0037] The heater 3 is, for example, a heating apparatus, and a heating temperature of the heater 3 is adjusted by an external control part during film-forming, and the substrate 2 is heated to a desired temperature. In the present invention, it is an object to lower a temperature, and for example, the substrate 2 is heated at a temperature between 120 C. and 300 C. by the heater 3.

[0038] A raw material solution (hereinafter, referred to as a solution) 4 for film-forming a Zn.sub.1-xAl.sub.xO film serving as a buffer layer is filled into the solution container 5. The solution 4 contains zinc (Zn) and aluminum (Al) as a metal source (mixed crystal in the film to be film-formed). More specifically, the solution 4 contains a metal compound having zinc and aluminum. Herein, the metal compound is, for example, a -diketone compound (acetylacetonato).

[0039] As a solvent of the solution 4, water, alcohols such as methanol or other organic solvent, or mixed solution of these liquids can be employed.

[0040] For example, an ultrasonic atomizer can be employed as the mist generator 6. The mist generator 6 which is the ultrasonic atomizer forms the solution 4 in the solution container 5 into a mist by applying an ultrasonic wave to the solution 4 in the solution container 5. The mist of the solution 4 is supplied to the reaction container 1 through a path L1.

[0041] Then, the solution 4 atomized in the reaction container 1 is sprayed to the substrate 2 being heated to film-form a Zn.sub.1-xAl.sub.xO film serving as a buffer layer on the substrate 2. Here, the solution 4 which is left unreacted in the reaction container 1 is discharged out of the reaction container 1 all the time (in a continuous manner) through the path L3.

[0042] Next, a method for film-forming a buffer layer of the present embodiment will be described

[0043] At first, a solution 4 including zinc and aluminum is prepared. Here, when the amount of aluminum in the solution 4 relative to the amount of zinc in the solution 4 is varied, the resistivity and the band gap of a buffer layer to be film-formed vary.

[0044] Specifically, when in the solution 4, the amount of aluminum relative to the amount of zinc is increased, the resistivity of a buffer layer to be film-formed is increased and the band gap of the buffer layer to be produced is increased.

[0045] Accordingly, the content of aluminum relative to the content of zinc is adjusted in the solution 4 so that a buffer layer having a desired resistance value and a desired band gap is film-formed.

[0046] The prepared solution 4 is formed into a mist by the mist generator 6 in the solution container 5. The mist of the solution 4 is supplied to the reaction container 1 through a path L1.

[0047] On the other hand, the substrate 2 is heated to a predetermined temperature by the heater 3, and a heating temperature of the substrate 2 is maintained at a predetermined temperature. For example, the heating temperature of the substrate 2 is maintained, for example, at any temperature of about 120 C. to 300 C.

[0048] The mist-like solution 4 is sprayed to the substrate 2 being heated. Thereby, a Zn.sub.1-xAl.sub.xO film serving as a buffer layer is film-formed on the substrate 2 existing in the reaction container 1. Here, a value of x satisfies a relationship of 0 <x <1 and varies according to a content ratio of (Al/Zn) in a solution 4 to be prepared.

[0049] Further, as described above, the mist of the solution 4 is sprayed to the substrate 2 disposed in the atmosphere.

[0050] As described above, in the method for film-forming a buffer layer of the present embodiment, a mist method in which the solution 4 is sprayed to the substrate 2 disposed in the atmosphere is employed.

[0051] Thus, in the film-forming method, since a pressure in the reaction container 1 does not need to be reduced and the mist of the solution 4 which is liquid is used for film-forming instead of gas, the buffer layer can be film-formed by a process step which is simple and low in cost.

[0052] Further, when the buffer layer is film-formed by the solution growth method, a large apparatus for immersing a substrate is required in the case of film-forming a large area of a buffer layer, and upsizing of an apparatus has been seen as a problem However, in the film forming apparatus 100, it is possible by the mist method to make an apparatus smaller than the apparatus in which the solution growth method is implemented.

[0053] Also, when the buffer layer is film-formed by the solution growth method, film-formation is vulnerable to various interference in a reaction process, and it has been difficult to bring the reaction into equilibrium at one point. Therefore, in the buffer layer prepared by the solution growth method, the controllability of a band gap was deteriorated (that is, the buffer layer having a band gap which is different in its value from a band gap of an aimed value was film-formed).

[0054] However, in the method for film-forming a buffer layer of the present embodiment, a mist method is employed. Accordingly, the film-forming is hardly vulnerable to interference. Therefore, it is possible to film-form a buffer layer having a band gap of an aimed value on the substrate 2 by only adjusting the content ratio of (Al/Zn) in the solution 4 (that is, the method is excellent in controllability of a band gap).

[0055] Further, for example, when the buffer layer of the present invention is film-formed by a CVD method, it is necessary to vaporize an organic metal solution such as diethyl zinc. This leads to complicated constitution of a production apparatus or an increase in production cost.

[0056] In contrast with this, in the present invention, the solution 4 can be prepared by using an inexpensive and stable compound, for example, a -diketone metal compound, and the solution 4 has only to be formed into a mist. Therefore, the film-forming method according to the present invention can film-form the buffer layer by a process step which is more simple and lower in cost than the film-forming method using the CVD method.

[0057] In addition, ozone may be supplied, in addition to spraying of the mist of the solution 4, to the reaction container 1 in which the substrate 2 being heated is disposed. FIG. 2 is a view showing a schematic configuration of a film forming apparatus for a buffer layer 200 which also supplies ozone.

[0058] As is apparent from the comparison between FIG. 1 and FIG. 2, the film forming apparatus 200 has the configuration in which an ozone generator 7 is added to the configuration of the film forming apparatus 100. Further, in the film forming apparatus 200, a path L2 which is a separate path from the path L1 is disposed in order to supply ozone from the ozone generator 7 to a reaction container 1.

[0059] The configuration of the film forming apparatus 200 is similar to that of the film forming apparatus 100 except for adding the ozone generator 7 and the path L2.

[0060] The ozone generator 7 can generate ozone. Thus, ozone generated by the ozone generator 7 passes through the path L2 different from the path L1 and is supplied into the reaction container 1. In the ozone generator 7, for example, an oxygen molecule is decomposed by applying a high voltage between parallel electrodes disposed in parallel and passing oxygen between the electrodes, and ozone can be generated by coupling the decomposed oxygen with another oxygen molecule.

[0061] In the film forming apparatus 200, ozone and the mist-like solution 4 are supplied to the reaction container 1 in which the substrate 2 being heated is disposed. Here, ozone and the solution 4 which are left unreacted in the reaction container 1 are discharged out of the reaction container 1 all the time (in a continuous manner) through the path L3. Further, the substrate 2 is disposed in the atmosphere.

[0062] The present inventors found that as described above, when ozone is supplied during film-forming a buffer layer, a desired buffer layer can be film-formed even though the heating temperature of the substrate 2 is lowered (e.g., 120 C. to 200 C.).

[0063] Further, in the film forming apparatuses 100 and 200, the solution 4 may contain ammonia. The present inventors found that by allowing the solution 4 to contain ammonia in this way, a desired buffer layer can be film-formed even though the heating temperature of the substrate 2 is lowered (e.g., 120 C. to 200 C.). Herein, the solution 4 may contain ammonia without supplying ozone; however, the solution 4 may contain ammonia and may further be supplied with the ozone.

[0064] In addition, the present inventors allows the solution 4 to contain ammonia in a molar ratio NH.sub.3/Zn of about 22.2) and film-forms a buffer layer using a film forming apparatus 200 shown in FIG. 2 (that is, by supplying ozone to a reaction container 1). Further, a film-forming temperature is in a range of 120 C. to 300 C. Here, the buffer layer can be film-formed even at a temperature higher than 300 C.; however, an experiment was omitted from the viewpoint of lowering a temperature. Further, the buffer layer could not be sometimes film-formed at the film-forming temperature less than 120 C.

[0065] FIG. 3 shows the results at the time when a plurality of buffer layers were prepared varying the content of Al relative to the content of Zn and varying the film-forming temperature, and band gap values (eV) of the buffer layers were measured.

[0066] As shown in FIG. 3, Al/(Al+Zn) in the solution 4 is varied to 0, 0.1, 0.2, 0.35, and 0.5 by varying the amount of Al.

[0067] Here, the film-formation of the buffer layer was performed varying the film-forming temperature in the condition of Al/(Al+Zn)=0.75. The buffer layer was film-formed at each film-forming temperature; however, a value of a band gap of each buffer layer is over an upper limit of a measuring instrument. Accordingly, in FIG. 3, a band gap value of the buffer layer which was film-formed in the condition of Al/(Al+Zn)=0.75, is not shown.

[0068] Further, as shown in FIG. 3, film-formation of the buffer layers was performed varying the film-forming temperature to 120 C., 150 C., 200 C., 250 C., and 300 C. In addition, the film-formation of the buffer layer was not performed at the film-forming temperatures of 150 C., 200 C., 250 C., or 300 C. in the condition of Al/(Al+Zn)=0.35.

[0069] As is apparent from FIG. 3, the value of a band gap of the buffer layer film-formed is increased by increasing the additive amount of aluminum. In the range of the results of FIG. 3, the band gap value of the buffer layer (Zn.sub.1-xAl.sub.xO film) can be varied at least in the range of 3.52 eV to 4.25 eV by varying the additive amount of aluminum and the film-forming temperature. That is, in the buffer layer according to the present invention, the band gap can be controlled over a wide range.

[0070] FIG. 4 shows the results at the time when a plurality of buffer layers were prepared varying the content of Al relative to the content of Zn and varying the film-forming temperature, and resistivity (.Math.cm) of the buffer layers were measured.

[0071] As shown in FIG. 4, Al/(Al+Zn) in the solution 4 is varied to 0, 0.1, 0.2, 0.35, 0.5, and 0.75 by varying the amount of Al.

[0072] Further, as shown in FIG. 4, film-formation of the buffer layers was performed varying the film-forming temperature to 120 C., 150 C., 200 C., 250 C., and 300 C. In addition, the film-formation of the buffer layer was not performed at the film-forming temperatures of 150 C., 200 C., 250 C., or 300 C. in the condition of Al/(Al +Zn) =0.35. Similarly, the film-formation of the buffer layer was not performed at the film-forming temperature of 120 C. in the condition of Al/(Al+Zn)=0.75.

[0073] As is apparent from FIG. 4, the resistivity of the buffer layer film-formed is increased by increasing the additive amount of aluminum. In the range of the results of FIG. 4, the resistivity of the buffer layer (Zn.sub.1-xAl.sub.xO film) can be varied at least in the range of 8.010.sup.1 .Math.cm to 2.210.sup.7 .Math.cm by varying the additive amount of aluminum and the film-forming temperature. That is, in the buffer layer according to the present invention, the resistivity can be controlled over a wide range.

[0074] In addition, from values of the resistivity shown in FIG. 4, it is found that the buffer layer according to the present invention is neither a conductive body nor an insulating body, and is a substance having an electric conductivity intermediate between the conductive body and the insulating body.

[0075] FIG. 5 shows the results of detecting, with an energy dispersive X-ray analyzer (EDX apparatus), compositional ratios of the buffer layers (Zn.sub.1-xAl.sub.xO films) in which the above-mentioned measurement was performed.

[0076] That is, buffer layers (Zn.sub.1-xAl.sub.xO films) were film-formed at each film-formation temperature (120 C., 150 C., 200 C., 250 C., 300 C.) using each of solutions 4 whose Al/(Al+Zn) ratio are 0.1, 0.2, 0.35, 0.5 and 0.75 (that is, varying the content of aluminum relative to the content of zinc in the solution 4). Then, the compositional ratio (Al/(Al+Zn) EDX) of each of buffer layers (Zn.sub.1-xAl.sub.xO films) was measured using EDX apparatus. The measurement results are shown in a table of FIG. 5.

[0077] As is apparent from FIG. 5, when the solution 4 is allowed to contain zinc and aluminum as metal raw materials (to become a mixed crystal) and the buffer layer is film-formed using the solution 4, the film-formed buffer layer contains a predetermined amount of aluminum as a d crystal. That is, by using the solution 4, the Zn.sub.1-xAl.sub.xO film is film-formed.

[0078] In addition, the present inventors carried out the following experiments.

[0079] That is, the solution 4 is allowed to contain zinc and magnesium as metal raw materials and a film is film-formed using the solution 4. Here, the film-forming temperature was 150 C., and ammonia and ozone were supplied to a substrate during film-forming the film. Then, the band gap and the resistivity of the film-formed film were measured, and the compositional ratio of the film was also measured with use of an EDX apparatus.

[0080] Here, the content of magnesium relative to the content of zinc in the solution 4 was varied as follows. That is, a ratio Mg/(Mg+Zn) was 0, 0.17, 0.29, 0.375, 0.44, and 0.5.

[0081] The results of measuring the band gap and the resistivity of the films film-formed using the solution 4 are shown in FIG. 6.

[0082] As is apparent from FIG. 6, even when the content of magnesium relative to the content of zinc was varied in the solution 4, the band gap changed little. Also, even when the content of magnesium relative to the content of zinc was varied in the solution 4, changes in resistivity was small.

[0083] In addition, the compositional ratio of each film was measured with use of an EDX apparatus, and consequently magnesium was not detected in the film. From this, it is found that magnesium is contained little as a mixed crystal in the film-formed film. The reason for the measurement results of FIG. 6 (that is, even when the amount of magnesium in the solution 4 was varied, the band gap and the resistivity were not changed by large amounts in the film-formed film) is supposed that magnesium is contained little in the film.

[0084] In the buffer layer of the present invention, as shown in FIG. 5, aluminum is contained as a mixed crystal in the film-formed buffer layer. Accordingly, as shown in FIGS. 3 and 4, in the buffer layer film-formed, the band gap and the resistivity can be controlled over a wide range.

[0085] FIG. 7 is a table showing an average transmittance of the buffer layers (Zn.sub.1-xAl.sub.xO films) subjected to the above-mentioned measurement (FIGS. 3, 4).

[0086] That is, buffer layers (Zn.sub.1-xAl.sub.xO films) were film-formed at each film-formation temperature (120 C., 150 C., 200 C., 250 C., 300 C.) using each of solutions 4 whose Al/(Al+Zn) ratio are 0.1, 0.2, 0.35, 0.5, and 0.75 (that is, varying the content of aluminum relative to the content of zinc in the solution 4). Then, the transmittance of each of the buffer layers (Zn.sub.1-xAl.sub.xO films) was measured by irradiating the buffer layers with light of a predetermined wavelength (light of a plurality of wavelengths).

[0087] FIG. 7 shows an average transmittance which was obtained by irradiating each buffer film with light of a wavelength of 400 nm to 1500 nm (nearly a visible light region) to measure a transmittance and averaging the transmittances of the buffer films over the above-mentioned wavelength range. In addition, thicknesses of the buffer layers are about 500 nm to 700 nm.

[0088] In addition, as described above, the film-formation of the buffer layer was not performed at the film-forming temperatures of 150 C., 200 C., 250 C., or 300 C. in the condition of Al/(Al+Zn)=0.35. Similarly, the film-formation of the buffer layer was not performed at the film-forming temperature of 120 C. in the condition of Al/(Al+Zn)=0.75.

[0089] As is apparent from the results of FIG. 7 in each buffer layer, the average transmittance is about 90%, or 90% or more. This indicates that in the buffer layer according to the present invention, aluminum functions as a mixed crystal and does not function as a dopant. That is, when aluminum is contained as a dopant in a film of zinc oxide, the transmittance is reduced, but a reduction of the transmittance is not found in the buffer layer according to the present invention.

[0090] In addition, in the experiments concerning FIG. 7, the buffer layer was irradiated with light of a wavelength longer than 1500 nm to measure its transmittance. Consequently, the transmittance exceeding 80% was also maintained when irradiating the buffer layer with light of a wavelength of about 1500 nm to 1700 nm.

[0091] It has been described that the buffer layer according to the present invention is a Zn.sub.1-xAl.sub.xO film. In the ZnO film not containing Al, since an offset barrier is decreased, it is impossible to adequately perform a function as a buffer layer. On the other hand, in the AlO film not containing Zn, since the film becomes a complete insulating body, similarly, the film does not function as a buffer layer. Therefore, it is important for the buffer layer to have a constitution in which Al and Zn are contained in the film as a mixed crystal.

[0092] The present invention has been described in detail, the above-mentioned description is exemplifications in all aspects, and the present invention is not intended to be limited to these. Various modifications not exemplified are construed to be made without departing from the scope of the present invention.

REFERENCE SIGNS LIST

[0093] 1: reaction container [0094] 2: substrate [0095] 3: heater [0096] 4: raw material solution (solution) [0097] 5: solution container [0098] 6: atomizer [0099] 7: ozone generator [0100] 100,200: film forming apparatus [0101] L1,L2: path