CN110684948B - Alloy material set, CIGS target material, CIGS thin film and solar cell - Google Patents
Alloy material set, CIGS target material, CIGS thin film and solar cell Download PDFInfo
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- 238000001704 evaporation Methods 0.000 claims description 49
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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Abstract
The invention provides an alloy material group, which comprises three alloy materials, wherein the components are as follows: first alloy material: cu(0.01～1.0)In(0.01～1.0)Ga(0.01～1.0)Se(0.01～3.0)(ii) a The second alloy material: cu(0.01～2.0)In(0～1.0)Ga(0～1.0)Se(0.01～3.0)(ii) a A third alloy material: cu(0.01～2.0)In(0.01～1.5)Ga(0.01～1.0)Se(0.01～3.0)。
Description
Technical Field
The invention relates to the field of film preparation, in particular to an alloy material set, a CIGS target material, a CIGS film and a solar cell.
Background
Copper indium selenide (CuInSe)2CIS for short or CuInGaSe (CuIn)xGa1-xSe2CIGS for short) thin-film solar cells are one of the research hotspots of solar cell materials in various countries because the thin-film solar cells have high photoelectric conversion efficiency, relatively low manufacturing cost, stable performance, no light-induced decay and lower price than the traditional crystalline silicon cells.
How to improve the conversion efficiency of the CIGS thin-film solar cell is still one of the current research hotspots, and it is necessary to provide a CIGS target material and a CIGS thin film which can improve the conversion efficiency of the CIGS thin-film solar cell.
Disclosure of Invention
In view of the above, it is necessary to provide an alloy material set, a CIGS target, a CIGS thin film, and a solar cell, in order to improve the conversion efficiency of the CIGS thin film solar cell.
The invention provides an alloy material group, which comprises three alloy materials:
first alloy material: cu(0.01～1.0)In(0.01～1.0)Ga(0.01～1.0)Se(0.01～3.0)；
The second alloy material: cu(0.01～2.0)In(0～1.0)Ga(0～1.0)Se(0.01～3.0)；
A third alloy material: cu(0.01～2.0)In(0.01～1.5)Ga(0.01～1.0)Se(0.01～3.0)。
In one embodiment, the three alloy materials respectively have the following compositions:
first alloy material: cu(0.01～0.5)In(0.01～0.5)Ga(0.5～1.0)Se(0.01～3.0)；
The second alloy material: cu(1.0～2.0)In(0～0.5)Ga(0～0.5)Se(0.01～3.0)；
A third alloy material: cu(0.01～0.5)In(0.5～1.5)Ga(0.5～1.0)Se(0.01～3.0)。
In one embodiment, the second alloy material does not contain Ga.
In one embodiment, the second alloy material does not contain In element.
In one embodiment, the three alloy materials respectively have the following compositions:
first alloy material: cu0.1In0.3Ga1.0Se0.5；
The second alloy material: cu2.0Se0.5；
A third alloy material: cu0.1In0.5Ga1.0Se0.5。
The invention also provides a CIGS target material which comprises the alloy material group, wherein the CIGS target material at least comprises a first alloy target material, a second alloy target material and a third alloy target material, the first alloy target material comprises the first alloy material, the second alloy target material comprises the second alloy material, and the third alloy target material comprises the third alloy material. In one embodiment, the lengths of the first alloy target material, the second alloy target material and the third alloy target material along the first direction are all 1-5 m.
In one embodiment, a length of the first alloy target in the first direction is greater than lengths of the second alloy target and the third alloy target in the first direction.
In one embodiment, the first alloy target, the second alloy target, and the third alloy target are sequentially arranged along the first direction.
In one embodiment, the purity of each target is greater than or equal to 99.99%.
In one embodiment, the first alloy target and/or the third alloy target further include an alkali metal element, and a mass fraction of the alkali metal element in the first alloy target or the third alloy target is 0.01% to 0.1%.
The invention also provides a CIGS thin film which is obtained by evaporation of the CIGS target material, wherein the CIGS thin film comprises a first thin film layer, a second thin film layer and a third thin film layer which are sequentially stacked, and the CIGS thin film is obtained by sequentially evaporation of the first alloy target material, the second alloy target material and the third alloy target material.
In one embodiment, the first thin film layer has an energy band gap in a range of 1.3eV to 1.5eV, the second thin film layer has an energy band gap in a range of 0.9eV to 1.1eV, and the third thin film layer has an energy band gap in a range of 1.1eV to 1.3 eV.
In one embodiment, the first thin film layer has an energy band gap of 1.4V, the second thin film layer has an energy band gap of 1.0V, and the third thin film layer has an energy band gap of 1.2 eV.
In one embodiment, the composition of the first thin film layer is CuIn0.5Ga0.5Se2(ii) a The second thin film layer comprises CuInSe2The third thin film layer contains CuIn0.8Ga0.2Se2。
In one embodiment, the stoichiometry of the elements In the CIGS thin film corresponds to 0.2 ≦ Ga/(In + Ga) ≦ 0.4.
In one embodiment, the stoichiometry of the elements In the CIGS thin film corresponds to Ga/(In + Ga) ═ 0.3.
In one embodiment, the CIGS thin film assembly is CuIn0.7Ga0.3Se2。
In one embodiment, the first thin film layer of the CIGS thin film has a thickness greater than the thicknesses of the second and third thin film layers.
In one of the embodiments, the CIGS thin film layer has a graded profile of double band gaps.
The invention also provides a solar cell comprising the CIGS thin film.
The alloy material group is used for preparing a CIGS target material, and the CIGS target material is used for preparing a CIGS thin film with a multilayer structure. Compared with the traditional solar cell with a single CIGS film layer, the solar cell with the CIGS film with the multilayer structure can have larger open-circuit voltage and short-circuit current, so that the photoelectric conversion efficiency of the CIGS film solar cell is improved to a great extent.
Drawings
FIG. 1 is a schematic structural diagram of a thin film deposition apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic view of a heating device arrangement according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a thin film deposition apparatus according to another embodiment of the present invention;
fig. 4 is a schematic structural diagram of an annular thin film evaporation apparatus according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the thin film deposition apparatus and the thin film deposition method of the present invention will be described in further detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only. The various objects of the drawings are drawn to scale for ease of illustration and not to scale for actual components.
The embodiment of the invention provides an alloy material group, which comprises at least three alloy materials:
first alloy material: cu (copper)(0.01～1.0)In(0.01～1.0)Ga(0.01～1.0)Se(0.01～3.0)；
The second alloy material: cu(0.01～2.0)In(0～1.0)Ga(0～1.0)Se(0.01～3.0)；
A third alloy material: cu(0.01～2.0)In(0.01～1.5)Ga(0.01～1.0)Se(0.01～3.0)。
The alloy material group is used for preparing a CIGS target material, and the CIGS target material is used for preparing a CIGS thin film with a multilayer structure. Compared with the traditional solar cell with a single CIGS film layer, the solar cell with the CIGS film with the multilayer structure can have larger open-circuit voltage and short-circuit current, so that the photoelectric conversion efficiency of the CIGS film solar cell is improved to a great extent.
In a preferred embodiment, the three alloy materials have the following compositions:
first alloy material: cu(0.01～0.5)In(0.01～0.5)Ga(0.5～1.0)Se(0.01～3.0)；
The second alloy material: cu(1.0～2.0)In(0～0.5)Ga(0～0.5)Se(0.01～3.0)；
A third alloy material: cu(0.01～0.5)In(0.5～1.5)Ga(0.5～1.0)Se(0.01～3.0)。
The content and distribution of Cu, Ga and In elements In the CIGS thin film are controlled by adjusting the content of Cu, Ga and In elements In each alloy material, so that the energy band gap of a first thin film layer of the CIGS thin film evaporated by the alloy material group is In a range of 1.3 eV-1.5 eV, the energy band gap of a second thin film layer is In a range of 0.9 eV-1.1 eV, the energy band gap of a third thin film layer is In a range of 1.1 eV-1.3 eV, and the energy band gaps of three thin film layers stacked In the CIGS thin film prepared by the alloy material group are In double-band-gap gradient distribution In the thickness direction of the thin film. The open-circuit voltage and short-circuit current and conversion efficiency of a solar cell prepared by using the CIGS thin film are effectively improved.
In a preferred embodiment, the second alloy material does not contain In element, and the In element In the second thin film layer of the CIGS thin film may be provided by diffusion of the In element evaporated from the first alloy material and/or the third alloy material In the thin film formation apparatus, or by a separate In source material provided In the thin film evaporation apparatus (preferably, the amount of the separate In source is controlled so that the In content In the second thin film layer of the CIGS thin film is small). In another preferred embodiment, the second alloy material does not contain Ga, the second thin film layer of the CIGS thin film does not contain Ga, or contains a small amount of Ga, and when the second thin film layer of the CIGS thin film contains Ga, the Ga may be provided by diffusion of the Ga evaporated from the first alloy material and/or the third alloy material in the thin film evaporation apparatus, or by a separately present Ga source material in the thin film preparation apparatus (preferably, the amount of the separately present Ga source is controlled so that the Ga content in the second thin film layer of the CIGS thin film is small). By not including In and/or Ga elements In the second alloy material, more Cu and Se elements can be contained In the second thin film layer of the CIGS thin film, so that the surface of the second thin film layer of the CIGS thin film is In a copper-rich state.
In order to provide the CIGS thin film with a graded double band gap distribution, it is preferable that the first alloy material provides most (for example, 90% or more) of In and Ga elements (or may further provide a large amount of Se elements) In the CIGS thin film, the second alloy material provides most of Cu elements In the CIGS thin film, the third alloy material provides the remaining Cu, In and Ga elements (or may further provide the remaining Se elements) In the CIGS thin film, the element ratio of the surface of the CIGS thin film is finely adjusted, and the third thin film layer of the CIGS thin film is slightly In-rich and the total amount of the elements In the CIGS thin film is In a preset ratio. Preferred CIGS thin film assemblies are CuIn0.7Ga0.3Se2。
More preferably, the composition of the first alloy material is Cu0.1In0.3Ga1.0Se0.5(ii) a The composition of the second alloy material is Cu2.0Se0.5(ii) a The third alloy material comprises the component of Cu0.1In0.5Ga1.0Se0.5. Accordingly, the first alloy material is used for providing the thin film layer with the energy band gap of 1.4eV, the second alloy material is used for providing the thin film layer with the energy band gap of 1.0eV, and the third alloy material is used for providing the thin film layer with the energy band gap of 1.2 eV.
An embodiment of the present invention further provides a CIGS target, where the material of the CIGS target includes the alloy material set described above, the CIGS target includes at least a first alloy target, a second alloy target, and a third alloy target, the material of the first alloy target includes the first alloy material, the material of the second alloy target includes the second alloy material, and the material of the third alloy target includes the third alloy material.
In one embodiment, the first alloy target further includes an alkali metal element, and preferably, the alkali metal element included in the first alloy target exists in the form of an alkali metal simple substance or an alkali metal compound, and for example, may exist in the form of metal chloride such as NaF, KF, and the like. The alkali metal element is doped in the target material, so that the crystal structure in the CIGS thin film can be effectively optimized, and the thin film has a preferred orientation in a (112) direction. In addition, the cell prepared by using the CIGS thin film doped with the alkali metal element has higher open-circuit voltage and further has higher photoelectric conversion efficiency.
In another embodiment, the third alloy target further includes an alkali metal element, and preferably, the alkali metal element included in the third alloy target exists in the form of an alkali metal simple substance or an alkali metal compound, for example, it may exist in the form of NaF, KF, or the like, and the effect is substantially the same as the effect of the alkali metal element in the first alloy target.
In one embodiment, only the first alloy target or the third alloy target, or both of them, may be doped with alkali metal, and the content of alkali metal element in the first alloy target and/or the third alloy target may be adjusted according to the actual performance requirements of CIGS. Preferably, the mass fraction of the alkali metal element in the first alloy target or the third alloy target is 0.01% -0.1%, and the doping amount enables the prepared CIGS thin film to have a better open-circuit voltage.
In a preferred embodiment, the purity of the first alloy target, the second alloy target and/or the third alloy target is greater than or equal to 99.99% so as to ensure the uniformity of the prepared CIGS film and the consistency of the components of the CIGS film. The purity is that the mass ratio of the first, second and third alloy materials in the corresponding first, second and third alloy target materials is greater than or equal to 99.99%. In addition, the high-purity CIGS target can ensure that the impurities in the prepared CIGS thin film are less, and the performance stability of the CIGS thin film is ensured, so that the photoelectric conversion efficiency of the thin-film solar cell prepared from the CIGS thin film is improved.
In order to vary the content of each element in the obtained CIGS thin film at different thickness positions of the CIGS thin film, and even separate at least three thin film layers with different components, the lengths of the first alloy target, the second alloy target and the third alloy target in the first direction may be in the order of meters, for example, each target has a length of 1 meter (m) to 5 m. The widths of the first, second, and third alloy targets may be substantially the same.
Preferably, the length of the first alloy target is greater than the length of the second alloy target and the length of the third alloy target respectively. The first alloy target is used to provide most (e.g., 90% or more) of the In and Ga elements (and may also provide most of the Se element) In the CIGS thin film, and the length of the first alloy target is set to be long, so that the first alloy target can be used to provide enough In, Ga and Se elements without adjusting the movement rate of the substrate. Correspondingly, the thickness of the first thin film layer of the prepared CIGS thin film is larger than that of the second thin film layer and the third thin film layer.
The invention also provides a CIGS thin film which is obtained by evaporation of the CIGS target material containing the alloy material group, wherein the CIGS thin film comprises a first thin film layer, a second thin film layer and a third thin film layer which are sequentially stacked, and the CIGS thin film is obtained by sequentially evaporation of the first alloy target material, the second alloy target material and the third alloy target material. The first alloy target provides the majority of the first thin film layer, the second alloy target provides the majority of the second thin film layer, and the third alloy target provides the majority of the third thin film layer. In such a target arrangement, the first thin film layer has a relatively high energy band gap, the second thin film layer has a relatively low energy band gap, and the third thin film layer has a relatively high energy band gap, so that the energy band gaps in the thickness direction of the entire CIGS thin film are distributed in a dual gradient manner, thereby improving the conversion efficiency of a solar cell manufactured using the CIGS thin film.
At the same temperature, the evaporation rates of Cu, In, Ga and Se elements are not consistent, so that the partial pressures of vapor formed In the evaporation chamber by the Cu, In, Ga and Se elements are not consistent, and the finally formed components of the first thin film layer, the second thin film layer and the third thin film layer are not completely consistent with the components of the first alloy target, the second alloy target and the third alloy target. In addition, since the target material is diffused in a certain range in the thin film evaporation device after being heated and evaporated, the components of the first thin film layer, the second thin film layer and the third thin film layer in the CIGS thin film do not completely correspond to the corresponding first alloy target material, the second alloy target material and the third alloy target material. In consideration of the characteristics which are not completely corresponding but are mutually related, the embodiment of the invention controls the content of elements in the three alloy targets in a proper range to enable the obtained three-layer film to have a perfect composition, and preferably realizes the gradient distribution of double band gaps.
Preferably, the stoichiometry of the elements In the CIGS thin film corresponds to 0.2 ≦ Ga/(In + Ga) ≦ 0.4, and In a preferred embodiment, the stoichiometry of the elements In the CIGS thin film corresponds to Ga/(In + Ga) ≦ 0.3.
In one embodiment, Ga/(In + Ga) In the thin film exhibits a V-shaped distribution In the thickness direction of the CIGS thin film, thereby enabling an increase In the open-circuit voltage and short-circuit current of the CIGS thin film, thereby increasing the conversion efficiency of a cell using the CIGS thin film.
In one embodiment, the first thin film layer has an energy band gap ranging from 1.3eV to 1.5eV, the second thin film layer has an energy band gap ranging from 0.9eV to 1.1eV, and the third thin film layer has an energy band gap ranging from 1.1eV to 1.3 eV. In a preferred embodiment, the energy band gap of the first thin film layer is 1.4V, the energy band gap of the second thin film layer is 1.0V, and the energy band gap of the third thin film layer is 1.2 eV. The energy band gaps of the three thin film layers are different, and are reduced and then increased in the thickness direction of the CIGS thin film, namely, the CIGS thin film battery is in double-band-gap gradient distribution, so that the conversion efficiency of the CIGS thin film battery is effectively improved.
In a preferred embodiment, the composition of the first thin film layer is CuIn0.5Ga0.5Se2(ii) a The second thin film layer comprises CuInSe2The third thin film layer contains CuIn0.8Ga0.2Se2。
In one embodiment, the CIGS thin film is a graded profile thin film with a double band gap.
Another aspect of the present invention provides a solar cell including any one of the CIGS thin films described above.
Through tests, the open-circuit voltage of the solar cell prepared by using the CIGS thin film in one embodiment is improved by 5% and the short-circuit current is improved by 30% compared with the traditional solar cell prepared by using the CIGS thin film with a single film layer. Because the conversion efficiency of the solar cell is in positive correlation with both the open-circuit voltage and the short-circuit current, the conversion efficiency of the solar cell prepared by using the CIGS thin film is obviously improved compared with the conversion efficiency of the solar cell prepared by using the CIGS thin film with a single film layer in the prior art.
The embodiment of the invention also provides a film evaporation method, which comprises the following steps:
s1: in a film evaporation device, a plurality of targets with different components are arranged along a first direction;
s2: and evaporating the target while the substrate and the target move relatively in the first direction, and depositing to form a film on the substrate.
The plurality of compositionally different targets are preferably heated to the same temperature. Preferably, the plurality of targets with different compositions include the first alloy target, the second alloy target, and the third alloy target, which are sequentially arranged along a length direction, that is, a first direction, so as to obtain the CIGS thin film.
The method comprises the steps that at least three alloy targets are sequentially arranged along a first direction, the three targets are sequentially deposited at the same position of a substrate through the relative movement of the targets and the substrate, so that a CIGS thin film with components changing along with the thickness is deposited, and the finally prepared CIGS thin film has double-band-gap gradient distribution through adjusting the components of the targets according to the characteristic that different elements have different evaporation rates at the same temperature, so that the conversion efficiency of a solar cell prepared through the CIGS thin film can be effectively improved.
In a more preferred embodiment, in the thin film evaporation method, the length of each target is 1 m-5 m, and the relative movement speed of the target and the substrate to be evaporated is less than or equal to 3 m/min. More preferably, the relative motion between the target and the substrate is uniform, and of course, the relative motion may be non-uniform according to the consumption of the target or the actual demand of the substrate evaporation, and may be adjusted according to the actual process demand. The distance between the target and the substrate is 5-50 mm, preferably 10-35 mm; more preferably, it is 15mm to 25mm, and the pitch is set so that the composition of each plating layer is uniform and stable.
Preferably, the step S1 includes fixedly disposing the plurality of targets with different compositions on the same target fixing device along the first direction.
In one embodiment, step S2 includes receiving the substrate by a substrate carrier and moving the substrate in a first direction. Preferably, the substrate carrying device adsorbs the substrate by magnetic force or vacuum adsorption and drives the substrate to move along the first direction.
In a preferred embodiment, the target fixing device and the substrate carrying device are both flat, the substrate carrying device has a flat carrying surface for carrying the substrate, the target fixing device and the substrate carrying device are arranged in parallel, and the length directions of the target fixing device and the substrate carrying device are the same.
Preferably, the target further includes a buffer layer target, and the buffer layer target is a last target and is disposed at ends of the plurality of targets with different compositions along the first direction.
After the evaporation of the CIGS thin film is finished on the substrate, the buffer layer can be continuously evaporated under the condition of not taking out a sample, and the oxidation of the CIGS thin film on the substrate is further prevented. Preferably, the composition of the buffer layer target material is solid sulfide, and more preferably, the composition of the buffer layer target material is CdS. In another preferred embodiment, the thin film evaporation method further includes feeding H into the thin film evaporation apparatus while performing step S22S gas, and the buffer layer target is capable of reacting with H2S gas generates metal target material of sulfide layer at high temperature, preferably Cd target material, Cd steam and H formed by thermal evaporation2And reacting the S gas to generate the CdS buffer layer. By forming the evaporation buffer layer, the vacuum degree in the cavity can be effectively reduced, and the gaseous substance in the cavity forms stable air pressure, so that the components and the thickness of the buffer layer deposited on the substrate are more uniform.
Preferably, the evaporation temperature of the target is 500 to 1100 deg.C, more preferably 600 to 1000 deg.C, and still more preferably 700 to 900 deg.C, and in such a temperature range, the evaporation rate of the target is more stable, enabling the evaporation gas to be uniformly deposited on the substrate. In a preferred embodiment, the plurality of targets are heated to the same temperature, so that the evaporation rate of each target is uniform, which makes the deposition of the target composition on the substrate more uniform.
In another embodiment, the target fixing device has a cylindrical sidewall for fixing the target, the first direction is a circumferential direction of the cylindrical sidewall, the substrate bearing device is sleeved outside the target fixing device and has an arc-shaped bearing surface coaxially arranged with the cylindrical sidewall for bearing the substrate, and the target is fixed on a side of the target fixing device facing the substrate bearing device. The substrate moves from one end of the opening of the arc-shaped plate to the target direction, and moves out from the other end of the arc-shaped plate after circling for a circle. In this way, the technological process of film evaporation greatly reduces the floor area of the production equipment.
According to the film evaporation method, the plurality of targets with different components are arranged along the first direction, and then the substrate and the targets are relatively displaced in the first direction, so that the materials of the plurality of targets are sequentially evaporated on the substrate to directly form the plurality of coating layers.
In some preferred embodiments, the thin film evaporation method is implemented by using a thin film evaporation apparatus described below.
Referring to fig. 1 and fig. 2, an embodiment of the invention provides a thin film evaporation apparatus, including:
a target fixing device 100 for fixing a plurality of targets 300 having different compositions in a first direction;
the substrate bearing device 200 is used for bearing a substrate to be coated and enabling the substrate to be arranged opposite to the target 300; and
a heating device 400 for heating the target 300 to evaporate the material of the target 300 on the substrate to form a thin film;
the target fixing device 100 and the substrate carrying device 200 can make the target 300 and the substrate move relatively along the first direction.
According to the film evaporation device, the target material fixing device 100 is used for fixing the target materials 300 with different components, then the substrate and the target material 300 are relatively displaced, and the components of the target material 300 are sequentially evaporated on the substrate to directly form a plurality of laminated coating layers, so that the substrate does not need to be exposed in the air in the evaporation process of the plurality of coating layers, and the problem that the evaporation coating layer is easily oxidized is effectively avoided.
In one embodiment, the heating device 400 is disposed on the side of the target fixing device 100 in the length direction, and preferably, the heating device 400 is disposed on both sides. Preferably, the heating device 400 comprises a heating source 401, the heating source 401 is an optical radiation heat source, more preferably, the heating source 401 is a quartz lamp, and the shape of the quartz lamp is adapted to the shape of the target fixing device 100; the length direction of the quartz lamp is identical to the length direction of the target fixing device 100. In a preferred embodiment, the heating apparatus 400 further includes a shadow mask 403, the shadow mask 403 is disposed on a side of the light radiation heating source 401 away from the target fixing apparatus 100, and controls a heat radiation direction of the heating source 401 toward the target fixing apparatus 100, that is, the heat radiation direction is toward the target 300. Alternatively, the heating device 400 provides heating in the range of 500 ℃ to 1100 ℃, preferably 600 ℃ to 1000 ℃, and more preferably 700 ℃ to 900 ℃, in which the evaporation rate of the target material is more stable, enabling the evaporation component to be uniformly deposited on the substrate.
Preferably, the heating device 400 is provided with one heating source 401, the heating source of the heating device 400 can heat a plurality of targets 300 with different components at the same time, and heat a plurality of targets 300 to the same temperature, so that the targets 300 generate steam, the evaporation temperatures of the targets 300 are consistent, the uniformity of each coating of the coating is ensured, and the heating cost in the production process is greatly reduced.
The target fixing device 100 and the substrate carrying device 200 can make the facing surfaces of the target 300 and the substrate parallel to each other.
In a preferred embodiment, the target fixing device 100 and the substrate supporting device 200 are both flat, the substrate supporting device 200 has a flat supporting surface for supporting the substrate, the target fixing device 100 is parallel to the substrate supporting device 200, and the length directions of the target fixing device 100 and the substrate supporting device 200 are the same. Accordingly, the quartz lamp is a straight quartz lamp, so that the heating temperature of each target 300 is uniform, and the substrate to be evaporated can be directionally moved by the power provided by the substrate carrying device 200, preferably, moved along a first direction, and sequentially passes through the targets 300 fixedly arranged on the target fixing device 100.
Preferably, the substrate is a stainless steel substrate, and correspondingly, the substrate carrying device 200 includes a conveyor belt, a magnetic block is disposed on the conveyor belt, the stainless steel substrate is attracted to and fixed on the conveyor belt by the magnetic block, and when the conveyor belt is in a moving state, the magnetic block moves along with the conveyor belt and drives the stainless steel substrate to move together with the stainless steel substrate, so as to generate a relative movement with the target 300, so that a plurality of stacked films with different compositions can be sequentially deposited on the stainless steel substrate. In another preferred embodiment, the conveyor belt itself is a magnetic chain or a magnetic belt, the stainless steel substrate is directly attracted and fixed to the conveyor belt and moves along with the conveyor belt, and when the conveyor belt is in a moving state, the magnetic block moves along with the conveyor belt and drives the stainless steel substrate to move together with the stainless steel substrate, so that the stainless steel substrate and the target 300 generate relative movement, and films with different compositions can be sequentially deposited on the stainless steel substrate.
In another preferred embodiment, the substrate is sucked and fixed on the conveyor belt by a vacuum device, so that the substrate moves directionally along with the conveyor belt. The substrate may be a glass, quartz or polymer substrate.
Preferably, each target 300 has a length of 1m to 5m, and the speed of the relative movement of the target fixing device 100 and the substrate to be evaporated is less than or equal to 3 m/min. More preferably, the relative motion between the target fixing device 100 and the substrate is a uniform motion, and of course, the relative motion may also be non-uniform according to the consumption of the target 300 or the actual requirement of the substrate evaporation, and may be adjusted according to the actual process requirement.
Preferably, the target fixing device 100 includes a fixing plate and a plurality of metal plates, the plurality of metal plates are fixedly disposed on the fixing plate, and the plurality of metal plates are used for fixing the plurality of targets 300 to the fixing plate. Preferably, the metal plate is a stainless steel plate and/or a copper plate, the target 300 is fixed on the target fixing device 100 through the stainless steel plate and/or the copper plate, and the target 300 is fixed on the stainless steel plate and/or the copper plate by at least one selected from welding, brass high-temperature fusion bonding, and/or high-temperature diffusion.
In a preferred embodiment, the target 300 comprises a CIGS target, and preferably comprises the first alloy target 301, the second alloy target 302, and the third alloy target 303 arranged in sequence along a length direction of the target, i.e., a first direction.
Referring to fig. 3, preferably, the target 300 further includes a buffer layer target 304, and the buffer layer target 304 is disposed on a side of the third alloy target 303 away from the second alloy target 302 along the first direction, so that after the evaporation of the CIGS thin film on the substrate is completed, the buffer layer can be continuously evaporated without taking out a sample, thereby further preventing the oxidation of the CIGS thin film on the substrate. Preferably, the composition of the buffer layer target 304 is solid sulfide, and specifically, the composition of the buffer layer target 304 is CdS. In another preferred embodiment, the thin film evaporation apparatus further comprises H2S gas inlet device, the buffer layer target material is capable of being connected with H2S gas generates a metal target of a sulfide layer at high temperature, preferably a Cd target, and H gas generates a metal target of a sulfide layer at high temperature2The S gas introducing device can introduce H into the film evaporation device in the evaporation process2Cd steam and H formed by thermal evaporation of S gas2And reacting the S gas to generate the CdS buffer layer. By forming the evaporation buffer layer, the vacuum degree in the cavity can be effectively reduced, and the gaseous substance in the cavity forms stable air pressure, so that the components and the thickness of the buffer layer deposited on the substrate are more uniform.
Preferably, the film evaporation device further includes a cooling device, the target fixing device 100 itself may be used as a cooling device, and the cooling device may also be fixedly disposed on a side of the target fixing device 100 away from the target, the cooling device is configured to control the temperature of the target 300, and the cooling device may, on one hand, cool the back of the target 300 and control the temperature of the target 300, so that the main body of the target 300 is in a solid state, and on the other hand, may also control the temperature of the surface of the target 300, so as to control the evaporation rate of the target 300 within a proper range.
Preferably, the film evaporation device further comprises a temperature adjusting device, preferably, the temperature adjusting device is arranged on one side of the substrate bearing device 200, which is away from the substrate, and is used for providing energy required by heating or cooling for the substrate, so that the vapor can be uniformly deposited on the substrate to form a stable film, only one temperature adjusting device is needed in the process of evaporating the substrate with a plurality of layers of films, and the temperature control cost in the production process is greatly reduced.
Optionally, because the Se element has high volatilization speed and is easy to lose in the evaporation process, the thin film evaporation device also comprises a supply source of the Se element, and Se steam is continuously supplied into the chamber when the Se source is heated to 200-500 ℃, so that the vapor pressure of the Se steam in the chamber is larger than 50kpa, and the Se element can be continuously and uniformly deposited on the substrate.
Optionally, the consumption speed of In atoms In the CIGS target material is relatively high, an independent In source can be added near the CIGS target material, and In steam is continuously supplemented into the chamber when the surface of the In source is heated to 400-800 ℃.
Of course, the thin film deposition apparatus may be provided with a source for supplying Cu or Ga elements, depending on actual production requirements.
Referring to fig. 4, in another embodiment, the target fixing device 100 has a cylindrical sidewall for fixing the target, the first direction is a circumferential direction of the cylindrical sidewall, the substrate supporting device 200 is sleeved outside the target fixing device and has an arc supporting surface for supporting the substrate, the arc supporting surface is coaxially disposed with the cylindrical sidewall, and the target 300 is fixed on a side of the target fixing device 100 facing the substrate supporting device 200. The substrate moves from one end of the opening of the arc-shaped plate to the direction of the target 300, and moves out from the other end of the arc-shaped plate after circling a circle. In this way, the film evaporation device greatly reduces the floor area of the production equipment.
Preferably, the heating device 400 may be disposed at an axial position of the target fixing device 100, or at least one of two radial sides of the target fixing device 100, and when the heating device 400 is disposed at the axial position of the target fixing device 100, the heating source 401 is preferably a straight quartz lamp, and a length direction of the straight quartz lamp is consistent with an axial direction of the target fixing device 100; when the heating device 400 is disposed on at least one side of the radial side surface of the target fixing device 100, the heating source 401 is preferably an annular quartz lamp, and the center of the annular quartz lamp coincides with the axis of the target fixing device 100. In summary, the heating source 401 is only required to be in a form that can ensure that each target 300 can be uniformly heated.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (20)
1. The CIGS target material for evaporation is characterized by comprising an alloy material group, wherein the alloy material group comprises three alloy materials, and the components of the alloy materials are as follows: first alloy material: cu (0.01-1.0) In (0.01-1.0) Ga (0.01-1.0) Se (0.01-3.0); the second alloy material: cu (0.01-2.0) In (0-1.0) Ga (0-1.0) Se (0.01-3.0); a third alloy material: cu (0.01-2.0) In (0.01-1.5) Ga (0.01-1.0) Se (0.01-3.0); the CIGS target at least comprises a first alloy target, a second alloy target and a third alloy target, wherein the first alloy target comprises the first alloy material, the second alloy target comprises the second alloy material, and the third alloy target comprises the third alloy material.
2. The CIGS target as recited in claim 1, wherein the first alloy target, the second alloy target and the third alloy target each have a length in the first direction of 1 to 5 m.
3. The CIGS target as recited in claim 2 wherein the first alloy target has a greater length in the first direction than the second and third alloy targets.
4. The CIGS target as recited in claim 1 wherein the first alloy target, the second alloy target and the third alloy target are arranged in sequence along the first direction.
5. The CIGS target material as claimed in claim 1, wherein each target material has a purity of 99.99% or higher.
6. The CIGS target as claimed in claim 1, wherein the first alloy target and/or the third alloy target further comprises an alkali metal element, and the mass fraction of the alkali metal element in the first alloy target or the third alloy target is 0.01% to 0.1%.
7. CIGS target material as claimed in claim 1, wherein the three alloy materials have the respective compositions: first alloy material: cu (0.01-0.5) In (0.01-0.5) Ga (0.5-1.0) Se (0.01-3.0); the second alloy material: cu (1.0-2.0) In (0-0.5) Ga (0-0.5) Se (0.01-3.0); a third alloy material: cu (0.01-0.5) In (0.5-1.5) Ga (0.5-1.0) Se (0.01-3.0).
8. CIGS target material as claimed in claim 1, wherein the second alloy material does not contain Ga element.
9. The CIGS target material as claimed In claim 1, wherein the second alloy material does not contain In element.
10. CIGS target material as claimed in claim 1, wherein the three alloy materials have the respective compositions: first alloy material: Cu0.1In0.3Ga1.0Se0.5; the second alloy material: Cu2.0Se0.5; the third alloy material: Cu0.1In0.5Ga1.0Se0.5.
11. A CIGS thin film obtained by vapor deposition of the CIGS target according to any one of claims 1 to 10, wherein the CIGS thin film includes a first thin film layer, a second thin film layer, and a third thin film layer stacked in this order, and is obtained by vapor deposition of the first alloy target, the second alloy target, and the third alloy target in this order.
12. The CIGS thin film as recited in claim 11, wherein the energy band gap of the first thin film layer is in the range of 1.3 to 1.5eV, the energy band gap of the second thin film layer is in the range of 0.9 to 1.1eV, and the energy band gap of the third thin film layer is in the range of 1.1 to 1.3 eV.
13. The CIGS thin film as recited in claim 12, wherein the energy band gap of the first thin film layer is 1.4V, the energy band gap of the second thin film layer is 1.0V, and the energy band gap of the third thin film layer is 1.2 eV.
14. The CIGS thin film as recited in claim 11, wherein the first thin film layer has a composition of cuin0.5ga0.5se2; the second thin film layer has a composition of CuInSe2, and the third thin film layer has a composition of CuIn0.8Ga0.2Se2.
15. The CIGS thin film as recited In claim 11 wherein the stoichiometric number of elements In the CIGS thin film is 0.2 ≦ Ga/(In + Ga) ≦ 0.4.
16. The CIGS thin film as recited In claim 11 wherein the stoichiometry of the elements In the CIGS thin film corresponds to Ga/(In + Ga) of 0.3.
17. The CIGS thin film as recited in claim 11 wherein the assembly of the CIGS thin film is cuin0.7ga0.3se2.
18. The CIGS thin film as recited in claim 11 wherein the first thin film layer of the CIGS thin film has a thickness greater than the thickness of the second thin film layer and the third thin film layer, respectively.
19. The CIGS thin film as recited in claim 11 wherein the CIGS thin film layer has a graded profile of double band gap.
20. A solar cell comprising the CIGS thin film according to any one of claims 11 to 19.
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| CN117894881B (en) * | 2024-03-12 | 2024-07-12 | 深圳先进技术研究院 | Method for adjusting hole concentration of CIGS film or solar cell by utilizing multi-target sputtering |
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| CN101845612A (en) * | 2008-12-18 | 2010-09-29 | 维易科精密仪器国际贸易(上海)有限公司 | Linear deposition source |
| US20130309805A1 (en) * | 2012-05-17 | 2013-11-21 | Intermolecular, Inc. | Method of Fabricating High Efficiency CIGS Solar Cells |
| CN104766896A (en) * | 2015-04-14 | 2015-07-08 | 湖南共创光伏科技有限公司 | Copper indium gallium selenium thin film solar cell with gradient structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845612A (en) * | 2008-12-18 | 2010-09-29 | 维易科精密仪器国际贸易(上海)有限公司 | Linear deposition source |
| US20130309805A1 (en) * | 2012-05-17 | 2013-11-21 | Intermolecular, Inc. | Method of Fabricating High Efficiency CIGS Solar Cells |
| CN104766896A (en) * | 2015-04-14 | 2015-07-08 | 湖南共创光伏科技有限公司 | Copper indium gallium selenium thin film solar cell with gradient structure and preparation method thereof |
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