CN102446989B - Photovoltaic device and manufacture method thereof - Google Patents
Photovoltaic device and manufacture method thereof Download PDFInfo
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- CN102446989B CN102446989B CN201110309568.8A CN201110309568A CN102446989B CN 102446989 B CN102446989 B CN 102446989B CN 201110309568 A CN201110309568 A CN 201110309568A CN 102446989 B CN102446989 B CN 102446989B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 79
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 79
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 77
- FRLJSGOEGLARCA-UHFFFAOYSA-N Cadmium sulfide Chemical compound [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000004065 semiconductor Substances 0.000 claims abstract description 52
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052793 cadmium Inorganic materials 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 210000002381 Plasma Anatomy 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 230000003287 optical Effects 0.000 claims description 9
- 150000004772 tellurides Chemical class 0.000 claims description 4
- AQCDIIAORKRFCD-UHFFFAOYSA-N Cadmium selenide Chemical compound [Cd]=[Se] AQCDIIAORKRFCD-UHFFFAOYSA-N 0.000 claims description 3
- CXKCTMHTOKXKQT-UHFFFAOYSA-N Cadmium oxide Chemical compound [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002294 plasma sputter deposition Methods 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004771 selenides Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 159
- 239000010408 film Substances 0.000 description 83
- RPPBZEBXAAZZJH-UHFFFAOYSA-N Cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 34
- -1 cadmium tin Chemical compound 0.000 description 19
- 239000000203 mixture Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
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- 239000006096 absorbing agent Substances 0.000 description 10
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- 238000000137 annealing Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 229910052756 noble gas Inorganic materials 0.000 description 8
- 229910052733 gallium Inorganic materials 0.000 description 7
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 229910052714 tellurium Inorganic materials 0.000 description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
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- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 210000004027 cells Anatomy 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001552 radio frequency sputter deposition Methods 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- MRPWWVMHWSDJEH-UHFFFAOYSA-N Antimony telluride Chemical compound [SbH3+3].[SbH3+3].[TeH2-2].[TeH2-2].[TeH2-2] MRPWWVMHWSDJEH-UHFFFAOYSA-N 0.000 description 2
- QNWMNMIVDYETIG-UHFFFAOYSA-N Gallium(II) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 2
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- 238000002835 absorbance Methods 0.000 description 2
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- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- MCMSPRNYOJJPIZ-UHFFFAOYSA-N cadmium;mercury;tellurium Chemical compound [Cd]=[Te]=[Hg] MCMSPRNYOJJPIZ-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 238000005286 illumination Methods 0.000 description 2
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 2
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- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000000877 morphologic Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 description 2
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- 150000003346 selenoethers Chemical class 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
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- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N Gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 229910004262 HgTe Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- VCEXCCILEWFFBG-UHFFFAOYSA-N Mercury telluride Chemical compound [Hg]=[Te] VCEXCCILEWFFBG-UHFFFAOYSA-N 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N [O--].[Zn++].[In+3] Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- PKLGPLDEALFDSB-UHFFFAOYSA-N [SeH-]=[Se].[In+3].[Cu+2].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se] Chemical compound [SeH-]=[Se].[In+3].[Cu+2].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se] PKLGPLDEALFDSB-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical class [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 1
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- 239000011669 selenium Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003595 spectral Effects 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
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- ZOMNDSJRWSNDFL-UHFFFAOYSA-N sulfanylidene(sulfanylideneindiganylsulfanyl)indigane Chemical compound S=[In]S[In]=S ZOMNDSJRWSNDFL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 1
- GTLQJUQHDTWYJC-UHFFFAOYSA-N zinc;selenium(2-) Chemical compound [Zn+2].[Se-2] GTLQJUQHDTWYJC-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to photovoltaic device and manufacture method thereof.One aspect of the present invention provides a kind of device, comprising: substrate；First semiconductor layer；Transparent conductive layer；Transparent window layer.This transparent window layer includes cadmium sulfide and oxygen.This device has the fill factor more than about 0.65.Another aspect of the present invention provides the method manufacturing this device.
Description
Technical field
The present invention relates generally to photovoltaic art.Especially, the present invention relates to manufacture the layer of use in photovoltaic device
Method and the photovoltaic device thus manufactured.
Background technology
In principal focal point in the field of photovoltaic device one is that energy conversion efficiency is (from electromagnetic energy to electric energy or vice versa
As the same) raising.It is the abundantest in many local solar energys whole year in the world.Unfortunately, available solar energy does not typically have
It is efficiently used for producing electric power.Photovoltaic (" PV ") device converts light directly into electric power.Photovoltaic device is from computer and hands
The little energy conversion device of table uses in many application of the big energy conversion device of house, public utilities and satellite.
Additionally, the photovoltaic cell of routine or solaode and the cost of electric power produced by these batteries are general the most relatively
High.Such as, typical solaode is less than the conversion efficiency of percent 20.Additionally, solaode typically comprises
The multiple layers formed on substrate, thus solaode manufacture typically needs substantial amounts of process step.As a result, substantial amounts of place
Reason step, layer, interface and complexity add and manufacture time and the capital quantity that these solaodes need.
Photovoltaic device often suffers from the performance of the reduction caused due to light by the loss such as reflected and absorb.Therefore,
Research in the optical design of these devices includes that light is collected and capture, Spectral matching absorb and luminous energy lifting/lowering frequency conversion (up/
down light energy conversion).Minimizing in the mode of this loss in photovoltaic cell one is to comprise width
Band gap Window layer.It is known that the design of Window layer and structure should have the highest band gap to minimize suction in this area
Receive loss.This Window layer also should with absorber layers on material compatible mutually so that the boundary between absorber layers and this Window layer
Bread contains insignificant boundary defect state.Typically, cadmium sulfide (CdS) is used for manufacturing such as cadmium telluride (CdTe) and two copper selenides
Window layer in the photovoltaic cell of indium gallium (CIGS) solaode.One major defect of cadmium sulfide is its relatively low band
Gap, it causes the current loss in device.Thin cadmium sulfide layer is used to help to reduce the light caused by absorption in photovoltaic device
Loss.But, due to the existence of this thin cadmium sulfide layer, these photovoltaic devices exist such as absorber layers and transparent conductive oxygen
The problems such as the shunting between compound (TCO).In order to overcome inferior position above, high resistance transparent cushion is used to prevent this shunting.
It addition, the treatment conditions manufacturing some photovoltaic devices of the device such as including cadmium telluride are harsh, and these layers expose
In high temperature, therefore these layers are major criterions at the heat stability of high temperature.
Thus it still remains a need have poor efficiency and complicated solar energy conversion device and the long-standing problem of manufacture method
Improvement technical scheme.
Summary of the invention
One aspect of the present invention provides a kind of device, comprising: substrate；First semiconductor layer；Transparent conductive layer；Transparent
Window layer.This transparent window layer includes cadmium sulfide and oxygen.This device has the fill factor more than about 0.65.
Another aspect of the present invention provides a kind of device, comprising: top board；Transparent conductive layer；Including cadmium sulfide and oxygen
Transparent window layer, and include the first semiconductor layer of tellurides.This device has the fill factor more than about 0.65.
The still another aspect of the present invention provides a kind of device, comprising: substrate；The first quasiconductor including selenides
Layer；Including cadmium sulfide and the transparent window layer of oxygen；And transparent conductive layer.This device has the fill factor more than about 0.65.
The still another aspect of the present invention provides the method manufacturing photovoltaic device.The method includes: arrange on substrate
Bright conducting shell；This transparent conductive substrate arranges transparent window layer；And the first quasiconductor is set adjacent to this transparent window layer
Layer.The step arranging this transparent window layer is included in the target including that the interior offer of environment of oxygen includes semi-conducting material, executes this target
Add multiple DC pulse to form pulsed dc plasma；With this pulsed dc plasma sputter this target with will include cadmium and
The material of sulfur sprays into this plasma；And the film including this material is deposited on substrate.This target includes semi-conducting material, its
Including cadmium and sulfur.
Accompanying drawing explanation
When following detailed description (wherein similar symbol represents similar parts in whole accompanying drawing) referring to the drawings is read
Time, the feature of these and other of the present invention, aspect and advantage will become better understood, wherein:
Fig. 1 diagram manufactures the flow chart of the method for film according to an embodiment of the invention.
Fig. 2 illustrates the percent transmittance plot about wavelength of film according to an embodiment of the invention.
Fig. 3 illustrates the scanning electron micrograph of film according to an embodiment of the invention.
Fig. 4 illustrates the X-ray diffraction of film according to an embodiment of the invention.
Fig. 5 illustrates the schematic diagram of photovoltaic device according to an embodiment of the invention.
The schematic diagram of Fig. 6 diagram photovoltaic device according to another embodiment of the invention.
Fig. 7 illustrates the extinction coefficient plot about wavelength of film according to an embodiment of the invention.
Fig. 8 illustrate film according to an embodiment of the invention by the oxygen content of XPS measuring.
Detailed description of the invention
Although only some feature of the present invention is illustrated and described herein, those skilled in that art are it is appreciated that many is revised
And change.It is understood, therefore, that the claim enclosed is intended to cover all such modifications and changes, they fall into the present invention's
In true spirit.In the specification and in the claims, will quote many terms, these terms have following meanings.
Singulative " one " and " being somebody's turn to do " include a plurality of indication thing, unless the context clearly dictates otherwise.As herein
In the approximating language that uses in the specification and in the claims can be applicable to modify any quantificational expression, it can change permissibly
And it is not resulted in the change in the basic function that it is associated therewith.Therefore, the term such as such as " about " value modified is not limited to rule
Fixed exact value.In some instances, this approximating language may correspond to the degree of accuracy of the instrument for measuring this value.Similarly,
" do not have " to be used in combination with term, and number or the trace of unsubstantiality can be included, but still be considered as that this is not repaiied
The term of decorations.
As used herein, term "available" and " can be " indicate: the probability occurred in one group of situation；There is regulation
Character, characteristic or function；And/or can modify another verb (by expression associate with the verb modified ability, performance or
One or more in probability).Therefore, the term using instruction to be modified of "available" and " can be " can for indicate
Property, function or use be the most suitable, competent or suitable, but consider that the term of this modification in some cases may
It not the most suitable, competent or suitable.Such as, in some cases it may expected event or capacity, and at other
In the case of this event or capacity can not occur, this difference is correctly expressed by term "available" and " can be ".
" optional " or " alternatively " meaning is the event described subsequently or situation may or may not occur, and this description includes
Example that wherein event occurs and example that wherein event does not occurs.Term " includes ", " comprising " and " having " means and include
And look like and also can there is other element outside being in addition to the element listed.Additionally, whenever particularly unique feature of the present invention is recorded
For by least one in the many elements in group or time a combination thereof is constituted, understanding that this feature can include or by these in this group
Any element in element or combines with any element in other elements in this group constitute individually.
It is further appreciated that the such as term such as " top ", " bottom ", " outwards ", " inwardly " to be the word of convenience and do not explain
For restricted term.As used herein, term " disposed over " or " between being arranged on " refer to directly contact and pass through
There is between it interposed layer and indirectly fix or arrange.
As previously noted, one embodiment of the present of invention is the method for manufacturing film.The method includes: including oxygen
Environment in provide and include the target of semi-conducting material；This target is applied multiple DC pulse to form pulsed dc plasma；
This target is sputtered so that the material including cadmium and sulfur is sprayed into this plasma with this pulsed dc plasma；And this material will be included
The film of material deposits on substrate.
Fig. 1 represents flow process Figure 10 of the method for manufacture film according to an embodiment of the invention.Step 12 is the most heavy
The depositional environment in long-pending chamber provides substrate or top board (superstrate).In one embodiment, this substrate or top board can include
Glass, polymer, metal or complex.In another embodiment, this substrate can include depositing a layer over the substrate thoroughly
Bright conducting shell.In still another embodiment of the invention, this substrate or top board can include this substrate or the top board with multilamellar.These substrates
Or top board can be oriented by method known to a person skilled in the art or be fixed in this depositional environment, such as this substrate can lead to
The mode crossing support is fixed.
In step 14, target provides in oxygen environment.This target is the semi-conducting material including cadmium and sulfur.This target includes depositing
Semi-conducting material on substrate or top board.In one embodiment, this target is any semi-conducting material, and it includes having this
Character required by deposition containing cadmium and the compound of sulfur.In one embodiment, this target may also include zinc.Implement at another
In example, this target can farther include zinc oxide.In still another embodiment of the invention, this target includes by chemical molecular formula ZnxCd1-xS generation
The alloy of the zinc-cadmium sulfide of table, wherein x is the numeral in the scope from about 0.01 to about 0.99.An embodiment
In, this target can be placed in away from substrate or top board preset distance.
In one embodiment, during target can be placed in the environment of oxygen and the noble gas with estimated rate.A reality
Execute in example, the amount alterable of oxygen in this context and can from 0.1 to percent 50 about percent oxygen (based on volume or
By mass flow) scope in, to the ratio of oxygen and the noble gas mixtures of predeterminated level.The non-limit of spendable noble gas
Property example processed includes argon, helium, nitrogen and its combination.In one embodiment, the noble gas of employing is argon.An embodiment
In, the mixture of oxygen and noble gas can combine before introducing depositional environment and mix.In another embodiment, oxygen and
Noble gas can introduce in the depositional environment that mixing occurs respectively.Typically, the mixture of oxygen and noble gas is in depositional environment
Internal dividing potential drop maintains from about 0.1 Pascal to the scope of about 3 Pascals.
Step 16 involves the multiple DC pulse of applying in target to obtain pulsed dc plasma.As used herein, art
Language " pulsed sputter " is physical gas-phase deposite method, and its ion sputtering using target or magnetron sputtering produce coating from the teeth outwards
Or film.The example of the DC pulse that can put on target includes bipolar asymmetric pulses direct current power, its tens to hundreds of kilohertz
Hereby the frequency of (kHz) carrys out pulse.Typically those skilled in that art will be recognized by when DC pulse is at oxygen and noble gas
When environment puts on target, the ionization of gas also can occur.In step 18, target passes through this pulse direct current of pulsed sputter technique
Plasma sputtering is to spray into this plasma by the material including cadmium and sulfur.In one embodiment, this sputter at be in from
Pressure in the scope of about 0.1 Pascal to about 3 Pascals is carried out the mean power of about 500 watts.Real at another
Executing in example, this bipolar asymmetric pulses direct current power is about 100 KHz, and reversed time is at the model of about 3 microseconds to 4 microseconds
In enclosing, average power density is from the scope every about square centimeter 0.2 watt to every square centimeter 2 watts simultaneously.A reality
Executing in example, this sputters at the underlayer temperature being in from the scope of about 50 degrees Celsius to about 550 degrees Celsius and carries out, and
Some embodiments are carried out at the underlayer temperature from about 100 degrees Celsius to about 300 degrees Celsius.In another embodiment,
This sputters at ambient temperature and carries out.In one embodiment, the material sprayed from target when sputtering comprises cadmium and sulfur.Separately
In one embodiment, the material sprayed from target when sputtering in the environment of oxygen can comprise cadmium, sulfur and oxygen.
The method further provides for the step 20 for depositing on substrate or top board by the film of the material of ejection.It is deposited on
This film on substrate or top board includes cadmium and sulfur.In one embodiment, the film of this deposition farther includes oxygen, and it can be from coming from
The oxygen of target or come from the oxygen in surrounding and be included in this film.In still another embodiment of the invention, this film includes CdS1-yOy, its
Middle y changes to about 0.5 from about 0.001.In one embodiment, the film of this deposition has from about 1 atomic percent
Oxygen concentration to the scope of about 35 atomic percents.In another embodiment, film has from about 1 atomic percent
Oxygen concentration to the scope of about 25 atomic percents；And in a particular embodiment, this film has from about 5 atoms hundred
Proportion by subtraction is to the oxygen concentration in the scope of about 20 atomic percents.In one embodiment, the concentration of the oxygen in this film is at this film
It is inside uniform.In another embodiment, this film has the gradient of oxygen concentration in this film, and the meaning is the oxygen concentration in this film
Function as film thickness changes, and wherein this concentration is from the side (the most early material of deposition) at this film
First concentration change is to the second concentration at offside (material of the most later deposition).This change can be smooth and connect
Continuing, maybe this change can change as the series of discrete in oxygen concentration and exist.This gradient can be such as by deposition step
Process during the film deposition parameter such as the oxygen concentration changing such as surrounding and formed.In one embodiment, there is oxygen dense
This film of degree gradient has the first oxygen concentration in from about 0 atomic percent to the scope of about 10 atomic percents.?
In another embodiment, have this film of oxygen concentration gradient have from about 20 atomic percents to about 50 atomic percents
Scope in the second oxygen concentration.In one embodiment, this film can farther include zinc.
In one embodiment, the thickness of the film of deposition is at least about 10 nanometers.In another embodiment, the thickness of film
Degree is in from about 20 nanometers to the scope of about 200 nanometers.The deposition of film such as can be pressed by the many state modulator of balance
By force, between temperature, the energy source of use, sputtering power, pulse parameter, the size of target material and characteristic, target and substrate or top board
Distance or orientation in depositional environment of space and target material and position.The selection of sputtering power depend on substrate size and
Desired deposition.
In one embodiment of the invention, the method farther includes the step annealed by film.This annealing of film can be entered
Row continues about 1 minute to about 30 minutes.This annealing can be in the scope of about 100 degrees Celsius to about 550 degrees Celsius
Temperature is carried out.In still another embodiment of the invention, this annealing is carried out the temperature of about 200 degrees Celsius.
In one embodiment, this film is heat in the temperature from the scope of about 500 degrees Celsius to about 700 degrees Celsius
Stable.As used herein, term " thermally-stabilised " meaning is ought to be heated to the most about 500 degrees Celsius of grades be up to fixed temperature
When 10 minutes, the optical property of thermally-stabilised film, the such as wavelength in from about 400 nanometers to the scope of about 600 nanometers it
Between this film transmission curve under integral area relative between 400 nanometers and 600 nanometers of the film (or benchmark) not heated
The integral area of transmission of radiation be not changed more than percent 10 amount.Such as, for " thermally-stabilised " film, film is being exposed to
The integral area under transmission curve before and after high temperature will be not changed more than the amount of percent 10.An embodiment
In, for thermally-stabilised film, the such as optical property such as refractive index and/or extinction coefficient wavelength between 300 nanometers and 900 nanometers
In be not changed more than 10% amount.In one embodiment, film is in the scope from about 500 to about 700 degree centigrade
Temperature be heat-staple.In another embodiment, including cadmium sulfide and oxygen film from about 500 degrees Celsius to about
Temperature in the scope of 600 degree is heat-staple.In still another embodiment of the invention, including the film of cadmium sulfide and oxygen about 550
Degree Celsius temperature be heat-staple.As illustrated in fig. 2, even if when film is held by the annealing temperature of about 500 degrees Celsius
When continuous 10 minutes, this film has at least about percent in the wavelength in from about 300 nanometers to the scope of about 900 nanometers
The integrated transmission of 80.Additionally, as note from FIG. 2 that, hold about 500 degrees Celsius of annealing in the vacuum of about 20 millitorrs
After continuous 10 minutes, retain the blue shift of considerable mark compared with cadmium sulphide film with the film of oxygen including cadmium sulfide.It is also noted that 500
After degrees Centigrade 10 minutes, the integrated transmission of film does not change and exceedes about 6%.
In another embodiment, film has from the scope of about 2.3 electron-volts to about 3.1 electron-volts
Band gap.In certain embodiments, film has at the band from the scope of about 2.45 electron-volts to about 2.75 electron-volts
Gap.In one embodiment, the film deposited by this method has crystallite form, and it has the crystal grain less than about 100 nanometers
Size.In one embodiment, the film deposited by this method has nanocrystalline form.In another embodiment, film includes
Amorphousness.Typically, it may be noted that the form of film changes with the concentration of oxygen present in film.Such as, as illustrated in figure 3
, when the oxygen concentration in film increases to about 20 atomic percent, the form of film is dense from the oxygen with about 5 atomic percents
The crystallite morphologic change of degree is to amorphousness.This is supported by the data (Fig. 4) studied from x-ray diffraction further, wherein when
Oxygen concentration in film when 5 atomic percents increase to about 20 atomic percent, the form of film from crystallite morphologic change to non-
Crystal form state.
In yet another aspect, the present invention provides the device including depositing film as transparent window layer.As illustrated in Figure 5
, in one embodiment, it is provided that photovoltaic device 100.This device 100 include the most one or more layer 110,112,114,
The layers such as 116 and 118.In one embodiment, this photovoltaic device 100 include substrate 110 and be arranged on this substrate 110 transparent
Conducting shell 112.In the illustrated embodiment, transparent window layer 114 is arranged on this transparent conductive layer 112.A reality
Executing in example, the first semiconductor layer 116 is arranged on this transparent window layer 114.Back contact 118 is arranged on this first quasiconductor
On Ceng.
Because light 120 enters from supporter or substrate 110 and then passes into device, the layer illustrated in Figure 5
Configuration can be described as " top board " configuration.Because substrate 110 contacts with transparent conductive layer 112 in this embodiment, the general foot of substrate 110
Enough the most transparent visible ray is made to pass through substrate 110 and realize contacting with front contact layer 112.Substrate in the configuration of this diagram
The suitable examples of the material of 110 includes glass or polymer.In one embodiment, this polymer include clear polycarbonate or
Polyimides.Typically, substrate can include the substrate of any suitable material, and this suitable material includes but not limited to metal, partly leads
Body, doped semiconductor, amorphous dielectric, crystalline dielectric and its combination.
Electric current is transported external loading and transports device back by transparent conductive layer and back contact during operation, thus complete
Become circuit.The suitable material of transparent conductive layer 112 can include oxide, sulfide, phosphide, tellurides or its combination.This
A little transparent, conductive material can be doped or undoped.In one embodiment, transparent conductive layer 112 includes transparent conductive oxide,
Its example includes zinc oxide, stannum oxide, cadmium tin (Cd2SnO4), zinc-tin oxide (ZnSnOx), tin indium oxide (ITO), mix
The zinc oxide (ZnO:Al) of aluminum, zinc oxide (ZnO), the stannum oxide (SnO:F) of fluorine doped, titanium dioxide, silicon oxide, oxidation gallium indium tin
(Ga-In-Sn-O), zinc indium tin oxide (Zn-In-Sn-O), oxidation gallium indium (Ga-In-O), indium zinc oxide (Zn-In-O) and these
Combination.Suitably sulfide can include cadmium sulfide, indium sulfide etc..Suitably phosphide can include indium phosphide, gallium phosphide etc..
Typically, when light is fallen on solaode 100, the first semiconductor layer (otherwise referred to as " semiconductor absorber
Layer " or " absorber layers ") electronics in 116 is from more low-energy " ground state " (specific former wherein they are tied to solid
Son) it is energized into higher " excited state " (wherein they may move through solid).Because the energy in daylight and artificial light
Major part is in the visible range of electromagnetic radiation, and solar cell absorber should be in absorbing the radiation being in those wavelength
Efficiently.In one embodiment, the first semiconductor layer 116 includes tellurides, selenides, sulfide or its combination.Separately
In one embodiment, the first semiconductor layer 116 includes cadmium telluride, cadmium zinc telluride, cadmium telluride sulfur, cadmium manganese telluride or cadmium magnesium telluride.
Cadmium telluride (being otherwise referred to as " CdTe " in this article) thin film typically has heteromorphs.Additionally, it was found that cadmium telluride has height
Absorbance and in the band gap from about 1.45 electron-volts to about 1.5 electron-volt scopes.In one embodiment, telluride
The electronics of cadmium and optical property can change by forming cadmium telluride and such as other elements such as zinc, magnesium, manganese or the alloy of compound
Become.Although CdTe the most often uses in photovoltaic device and is not alloyed, but it can be alloyed.The film of CdTe can use
Low-cost technologies manufactures.In one embodiment, CdTe the first semiconductor layer 116 can typically comprise p-type crystal grain and N-shaped is brilliant
Boundary.
In certain embodiments, cadmium telluride can include other elements from race II and race VI or race III and race V, and it can
It is not resulted in big bandgap shifted.In one embodiment, for absorber layers, this bandgap shifted is less than or equal to about 0.1 electricity
Sub-volt.In one embodiment, the first semiconductor layer includes cadmium telluride, cadmium zinc telluride, rich tellurium cadmium telluride, cadmium telluride sulfur, tellurium
Cadmium manganese or cadmium magnesium telluride.In one embodiment, the atomic percent of the cadmium in cadmium telluride is from about 48 atomic percents
To the scope of about 52 atomic percents.In another embodiment, the atomic percent of the tellurium in cadmium telluride is from about
In the scope of 45 atomic percents to about 55 atomic percents.In one embodiment, the cadmium telluride of employing can include rich tellurium
Cadmium telluride, wherein the atomic percent of the tellurium in the cadmium telluride of this richness tellurium is from about 52 atomic percents to about 55
Material etc. in the scope of atomic percent.In one embodiment, the atomic percent of the zinc in cadmium telluride or magnesium is less than big
About 10 atomic percents.In another embodiment, the atomic percent of the zinc in cadmium telluride or magnesium is about 8 atomic percent
Ratio.In still another embodiment of the invention, the atomic percent of the zinc in cadmium telluride or magnesium is about 6 atomic percents.A reality
Executing in example, CdTe absorber layers 116 can include p-type crystal grain and N-shaped crystal boundary.
In one embodiment, the sulfuric horizon described before transparent window layer 114 includes above.It is arranged on the first conducting shell
Transparent window layer 114 on 116 is the knot cambium layer of device 100." freely " electronics in first conducting shell 116 is in random fortune
Dynamic, and the most typically it is likely not to have orientation direct current.But, the induction of adding of transparent window layer 114 produces the interior of photovoltaic effect
Build electric field.Transparent window layer 114 includes cadmium sulfide and oxygen, and in the scope from about 500 to about 700 degree centigrade
Temperature is heat-staple.In one embodiment, transparent window layer 114 can farther include zinc telluridse, zinc selenide, cadmium selenide,
Aska-Rid. sulfur and/or copper oxide.In another embodiment, transparent window layer includes CdS1-yOy, wherein y changes to from 0.01
0.5.In certain embodiments, the atomic percent of the cadmium in cadmium sulfide from about 48 atomic percents to about 52 atoms hundred
In the scope of proportion by subtraction.In one embodiment, the atomic percent of the sulfur in cadmium sulfide from about 45 atomic percents to greatly
In the scope of about 55 atomic percents.
In one embodiment, transparent window layer is included in from about 1 atomic percent to about 50 atomic percents
Oxygen in scope.In one embodiment, transparent window layer 114 has uniform oxygen concentration in Window layer 114.At another
In embodiment, transparent window layer 114 includes oxygen concentration gradient in transparent window layer 114.In one embodiment, this oxygen concentration
Gradient have in the interface with the first semiconductor layer 116 from about 0 atomic percent to the model of about 10 atomic percents
The first oxygen concentration in enclosing.In still another embodiment of the invention, this oxygen concentration gradient has in the interface with transparent conductive layer 112
The second oxygen concentration in from about 20 atomic percents to the scope of about 50 atomic percents.In one embodiment, should
Oxygen concentration gradient from the interface of transparent window layer 114 and transparent conductive layer 112 to transparent window layer 114 and the first semiconductor layer
The interface of 116 reduces in transparent window layer 114.In another embodiment, transparent window layer 114 can include bilayer, its bag
Include the layer of the cadmium sulfide with oxygen and include the second layer of the cadmium sulfide substantially free from oxygen.In one embodiment, transparency window
The layer that mouth double-deck 114 can be arranged so that including cadmium sulfide and oxygen forms interface with transparent conductive layer 112, and includes the layer of cadmium sulfide
Interface is formed with the first semiconductor layer 116.In one embodiment, transparent window layer 114 have from about 5 nanometers to about
Thickness in the scope of 250 nanometers, or the thickness in from about 20 nanometers to the scope of about 200 nanometers.Typically, first
Semiconductor layer 116 and transparent window layer 114 provide heterojunction boundary between these two layers.In certain embodiments, transparent window
Layer 114 serves as n-type window layer, and it forms pn-junction with p-type the first semiconductor layer.
Typically, back contact 118 or spreads out of incoming for electric current device 110 from it according to whole system configuration.Typically, the back of the body
Contact layer 118 includes metal, quasiconductor, graphite or other suitably electrically conductive materials.In one embodiment, back contact 118 wraps
Including quasiconductor, it includes p-type crystal grain and p-type crystal boundary.These p-type crystal boundaries will assist in back contacts metal and p-type semiconductor layer
Between transport charge carrier.In certain embodiments, back contact can include from zinc telluridse (ZnTe), telluride hydrargyrum (HgTe),
Cadmium mercury telluride (CdHgTe), arsenic telluride (As2Te3), antimony telluride (Sb2Te3) and telluride copper (CuxTe) in the quasiconductor selected in
One or more.
In certain embodiments, metal level (not shown) may be provided on back contact 118 for improving electrical contact.?
In some embodiments, it is one or more that this metal level includes in race's IB metal or race's IIIA metal or its combination.Race IB gold
The suitable non-limiting example belonged to includes copper (Cu), silver (Ag) and gold (Au).Race's IIIA metal (such as, low-melting-point metal)
Suitably non-limiting example includes indium (In), gallium (Ga) and aluminum (Al).Other examples of potential suitable metal include molybdenum and
Nickel.
In one embodiment, device can farther include the second semiconductor layer being arranged on the first semiconductor layer 116
(not shown).In one embodiment, this second semiconductor layer includes n-type semiconductor.This second semiconductor layer can include
The absorber layers of a part for photovoltaic device, the conversion of the electromagnetic energy of incident illumination (such as, daylight) to electric energy (that is, to electric current) exists
Wherein occur.Typically, the first semiconductor layer or absorber layers 116 may be provided in transparent window layer 114, and the second quasiconductor
Layer may be provided on the first semiconductor layer 116.First semiconductor layer 116 and this second semiconductor layer can be doped with p-type doping or n
Type adulterates, in order to form hetero-junctions etc..As used herein, term " hetero-junctions " is semiconductor junction, and it is partly led by dissimilar
The layer of body material is constituted.These materials are generally of unequal band gap.As example, hetero-junctions can pass through a conductance class
Contact between layer or region and layer or the region of contrary conductance of type is formed, such as " p-n " knot.This second semiconductor layer can be from
The II-VI compound semiconductor being built with band gap selects, such as cadmium zinc telluride, cadmium telluride sulfur, cadmium manganese telluride, cadmium mercury telluride, selenium
Cadmium or cadmium magnesium telluride.In one embodiment, this second semiconductor layer can include two copper indium gallium selenide (CIGS).Except solar energy
Outside battery, other devices of this hetero-junctions are utilized also to include thin film transistor (TFT) and bipolar transistor.
In some other embodiments, device can farther include high resistive transparent layer (not shown).An embodiment
In, this high resistive transparent layer may be provided on transparent conductive layer.In another embodiment, this high resistive transparent layer may be provided at transparent
Between conducting shell 112 and transparent window layer 114.This high resistive transparent layer can be from stannum oxide, zinc oxide, zinc-tin oxide (Zn-Sn-O)
Or zinc indium tin oxide (Zn-In-Sn-O) selects.In one embodiment, device does not include high resistive transparent layer.
In alternative as illustrated in Figure 6, " substrate " configuration includes that wherein back contact 118 is arranged on substrate
Photovoltaic device 200 on 110.Additionally, the first semiconductor layer 116 is arranged on this back contact 118.Including describe before
The transparent window layer 114 of sulfurized layer is then arranged on this first semiconductor layer 116 and transparent conductive layer 112 is arranged on this
In transparent window layer 114.In this substrate configures, this substrate can include glass, polymer or metal forming.An embodiment
In, the metal forming this metal forming can be used to include rustless steel, molybdenum, titanium and aluminum.In one embodiment, diagram in Fig. 6
The composition of layer (that is, substrate 110, transparent conductive layer 112, transparent window layer the 114, first semiconductor layer 116, back contact 118)
The identical composition with top board configuration having and describe the most in Figure 5.In one embodiment, the first semiconductor layer
116 can from curing copper and indium (CIS), two copper indium diselenide (CIS), two copper indium gallium selenide (CIGS), copper indium gallium sulphur selenium (CIGSS),
Copper and indium gallium aluminum sulfur selenium (Cu (In, Ga, Al) (Se, S)2), sulfide copper zinc tin (CZTS) and other systems based on CIS select.
Typically, the efficiency of solaode is defined to enter divided by battery surface from the electrical power of module extraction
The power density of the solar energy penetrated.Use Fig. 5 as reference, incident illumination 120 it in the first semiconductor layer 116 by absorption
Front by substrate 110, transparent conductive layer 112 and transparent window layer 114, luminous energy turning to electric energy in the first semiconductor layer 116
Change and occurred by the formation of electron hole pair.Four common performance metrics are had: (1) short-circuit current density for photovoltaic device
(JSC) be in zero and execute alive electric current density (2) open-circuit voltage (VOC) anode when being not have electric current to flow and negative electrode it
Between electromotive force.At VOC, all electronics and hole are compound in device.This point to can from Single Electron hole to extraction merit
It is provided with the upper limit.(3) fill factor (FF) equal to the peak power that can extract in operation and for battery at J based on itSC
And VOCAssessment under ratio between possible peak power.Energy conversion efficiency (η) depends on the optical delivery efficiency of device
With photoelectric transformation efficiency, and it is defined to:
η=JSCVOCFF/PS
Wherein (4) PSIt it is incident solar power.Pass shown in the equation ties up to determine the performance of solaode
In be made very well.But, three in molecule are not completely self-contained factors, and typically process at device, material or set
Particular refinement in meter can affect all three factor.
In one embodiment of the invention, device has the fill factor more than about 0.65.In another embodiment
In, device has the packed factor in the scope from about 0.65 to about 0.85.In still another embodiment of the invention, device tool
There is the open-circuit voltage (V more than about 0.81 voltOC)。
The still another aspect of the present invention provides the method manufacturing photovoltaic device.The method includes: arrange on substrate
Bright conducting shell；This transparent conductive substrate arranges transparent window layer；And this transparent window layer neighbouring arranges the first quasiconductor
Layer.It is identical with the method for the sulfuric horizon described before deposition that the step of this transparent window layer is set, and is commonly included in and includes
The target including semi-conducting material is provided in the environment of oxygen, this target is applied multiple DC pulse to form pulse direct current plasma
Body, sputters this target so that the material including cadmium and sulfur to spray into this plasma with this pulsed dc plasma, and will include
The film of this material deposits on substrate.This target includes semi-conducting material, and it includes cadmium and sulfur.
Example
Method 1: include the preparation of the film of cadmium sulfide and oxygen
Film including cadmium sulfide and oxygen uses cadmium sulfide target to prepare.This cadmium sulfide target is in 100kHz's by sputtering chamber
Frequency, the reversed time of 3.5 μ s and 1W/cm2The bipolar asymmetric DC pulse of average power density.This sputtering chamber maintains oxygen
With in the environment of argon；The oxygen using 0.05 produces the film including cadmium sulfide and oxygen to the flow rate ratio of argon, has in this film
Approximate the oxygen of 5 atomic percents.During this technique, the pressure of this sputtering chamber maintains 1.33 Pascals (10mTorr).Have
The flow rate ratio of oxygen is obtained by the film of the oxygen storage amount of change by changing argon.
Using the film preparing the cadmium sulfide not having any oxygen to above-described similar method, difference is this reality
In example, the environment of sputtering chamber is argon and does not has oxygen.
Film under the pressure of 3 Pascals at the annealing temperature 10 minutes of 500 degrees Celsius.As illustrated in the figure 7, find bag
The film of sulfur-bearing cadmium and oxygen is heat-staple, because they retain the blue shift of considerable mark after the heating.The film of these annealing
Heat stability also figure 8 illustrates, the most even when the film of the oxygen by having 5 atomic percents and 20 atomic percents is 550
Degree Celsius annealing temperature 10 minutes time, these films retain the oxygen of considerable mark.Typically, upon exposure to high temperature, oxygen will be from
Not there is heat-staple membrane diffusion go out, thus cause the decline in the band gap of film.
It is deposited on including the film of cadmium sulfide and oxygen and maintains about 200 degrees Celsius to the substrate of the temperature of 250 degrees Celsius.
Observe, be deposited on and maintain about 200 degrees Celsius of these films display absorbancies to the substrate of the temperature of 250 degrees Celsius
In (integral area between 400nm to 600nm), the increase of about 11% (maintains about 200 degrees Celsius to 250 with being deposited on
Degree Celsius temperature substrate on the absorbance of film of cadmium sulfide (not having oxygen) film compare).With distinct contrastly, CdS:O film is adopted
With such as at Mat.Res.Soc.Symp.Proc, rolling up 763,2003, the RF sputtering technology described in page B8.9.3-B8.9.4 is in dimension
Hold the deposition on the substrate of the temperature of 250 degrees Celsius and illustrate that ABSORPTION EDGE, along towards the more low-yield drift of about 7%, thereby indicates that
Reduction (when comparing with the transparency of CdS film) in transparency.
Method 2: there is the preparation of the cadmium telluride photovoltaic device of the transparent window layer including cadmium sulfide and oxygen
Cadmium telluride photovoltaic device by use close spaced sublimation technique about 500 degrees Celsius temperature coating cadmium sulfide
SnO2: the cadmium-telluride layer depositing about 3 microns on F TCO glass manufactures.This TCO glass obtains from Pilkington,
And it is coated with the SnO of 3 millimeters2: F forms coating SnO2: the soda-lime glass of F (has built-in high resistance transparent SnO2Layer
TEC10).SnO at coating cadmium sulfide2: the cadmium-telluride layer on F TCO glass is in atmosphere at the temperature chlorine of 400 degrees Celsius
Cadmium processes about 20 minutes.At the end of the time of regulation, the SnO being applied2: F TCO glass with copper solution process and
18 minutes are continued by the annealing temperature at 200 degrees Celsius.Then silver be deposited on the layer of this Copper treatment work by evaporation technology
For back contacts.
Different materials is used to prepare device as transparent window layer.Such as, in comparative example 1 (CEx.1), use
Pulsed sputter cadmium sulfide layer (temperature deposition at about 200 degrees Celsius to about 250 degrees Celsius) is as transparent window layer；Than
In relatively example 2 (CEx.2), use the cadmium sulfide using chemical bath deposition method (CBD) to deposit as transparent window layer；Show comparing
In example 3 (CEx.3), the cadmium sulfide of the temperature deposition using RF to sputter at about 200 degrees Celsius to about 250 degrees Celsius is used to make
For transparent window layer；And in comparative example 4 (CEx.4), use and use what RF sputtered at room temperature deposition to have about 10%
The cadmium sulfide of oxygen as transparent window layer.In example 1 (Ex.1), the pulsed sputter of the oxygen with 5atomic% is used to fill
Oxygen cadmium sulfide is as transparent window layer.The thickness of the transparent window layer in these five devices all maintains about 80 nanometers.
There is CdTe/CdS/HRT/SnO2: the photovoltaic device of the example 2 (Ex.2) of F device architecture uses above-described
Method 2 is prepared on low ferrum sodium lime glass.Transparent window layer in example 2 (Ex.2) is to have the thickness of 70nm, have
The pulsed sputter oxygenation cadmium sulfide of 10atomic% oxygen.The device of Ex.2 includes the SnO mixing zinc2High resistance transparent oxide layer
(HRT)。
There is CdTe/50nm CdS+80nm CdS:O (20%)/SnO2: the photovoltaic of the example 3 (Ex.3) of F device architecture
Device makes 2 preparations with the method outlined supra not have high resistance transparent oxide layer.The transparent window used in the device of example 3
Layer is the pulsed sputter oxygenation cadmium sulfide in transparent window layer with oxygen concentration gradient.
Form 1
Can notice from form 1, when there is no the device of oxygen in the transparent window layer in such as CEx.1 and CEx.2
Performance parameter when comparing, there is the increase in device display Jsc and Voc of the transparent window layer from Ex.1, have simultaneously
Good packed factor (FF).It may be noted that the device that the higher oxygen concentration found in CdS (Ex.3) has than CEx.1 is higher
Efficiency.When 70nm CdS:O (10atomic%) layer is used together with HRT layer, device example 2 (Ex.2) shows higher
Jsc and fill factor maintain high Voc simultaneously, thus provide higher efficiency.
Comparative example 3 and 4 (CEx.3 and CEx.4) be have include respectively RF sputtering cadmium sulfide and RF sputtering cadmium sulfide+
The device of the transparent window layer of 10atomic% oxygen.As shown in table 1, find that the device of CEx.3 and CEx.4 has greatly
The efficiency of about 10%.Although compared with CEx.3, the device of CEx.4 illustrates the Jsc of increase, but finds that fill factor reduces greatly
About 6% reduces about 10 millivolts to about 7% and Voc, thus causes the more inefficient of device.As
Mat.Res.Soc.Symp.Proc, rolls up 763,2003, described in page B8.9.1-B8.9.6, has RF sputtering CdS:O's
Increase in CdS/CdTe device display Jsc, but find that total device efficiency reduces with the minimizing in FF.This is attributable to transparent
The reduction in knot quality between Window layer and the first semiconductor layer.But, the pulsed sputter CdS:O film of the present invention illustrates raising
CdTe device performance.
This written explanation uses examples to disclose some embodiments of the present invention, and it includes optimal mode, and also makes this
In field, technical staff can put into practice the present invention, including manufacturing and use any device or system, and carries out any comprising
Method.The scope of the claims of the present invention is defined by the claims, and can include other examples that those skilled in that art expect.
If other examples such they there is not different from the written language of claim structural elements, if or they bag
Include written language with claim then to specify within the scope of the claims without the equivalent structural elements of substantive difference.
List of parts
| 10 | Method | 12 | Method step |
| 14 | Method step | 16 | Method step |
| 18 | Method step | 20 | Method step |
| 100 | Photovoltaic device | 110 | Substrate layer |
| 112 | Transparent conductive layer | 114 | Transparent window layer |
| 116 | First semiconductor layer | 118 | Back contacts |
| 120 | Light | 200 | Photovoltaic device |
Claims (9)
1. a photovoltaic device (100), comprising:
Substrate (110)；
First semiconductor layer (116)；
Transparent conductive layer (112)；And
Transparent window layer (114), it includes cadmium sulfide and oxygen, wherein, is being exposed to the model from 500 degrees Celsius to 700 degrees Celsius
During the temperature in enclosing 10 minutes, the optical property of described transparent window layer (114) is not changed more than the amount of percent 10,
And wherein said photovoltaic device (100) has the fill factor more than 0.65.
2. photovoltaic device as claimed in claim 1, wherein said transparent window layer (114) farther includes zinc telluridse, selenizing
Zinc, cadmium selenide, Aska-Rid. sulfur and/or copper oxide.
3. photovoltaic device as claimed in claim 1, wherein said transparent window layer (114) includes CdS1-yOy, wherein y is from 0.01
Change to 0.5.
4. photovoltaic device as claimed in claim 1, wherein said transparent window layer (114) includes the gradient of oxygen concentration.
5. photovoltaic device as claimed in claim 1, wherein said transparent window layer (114) have from 2.3 electron-volts to
Band gap in the scope of 3.1 electron-volts.
6. photovoltaic device as claimed in claim 1, wherein said transparent window layer (114) is included in from 0.1 atomic percent
Oxygen to the scope of 50 atomic percents.
7. a photovoltaic device (100), comprising:
Top board (110)；
Transparent conductive layer (112)；
Including the transparent window layer (114) of cadmium sulfide and oxygen, wherein, it is being exposed to the scope from 500 degrees Celsius to 700 degrees Celsius
In temperature 10 minutes time, the optical property of described transparent window layer (114) is not changed more than the amount of percent 10；
The first semiconductor layer (116) including tellurides；And
Wherein said photovoltaic device (100) has the fill factor more than 0.65.
8. a photovoltaic device (200), comprising:
Substrate (110)；
The first semiconductor layer (116) including selenides；
Including the transparent window layer (114) of cadmium sulfide and oxygen, wherein, it is being exposed to the scope from 500 degrees Celsius to 700 degrees Celsius
In temperature 10 minutes time, the optical property of described transparent window layer (114) is not changed more than the amount of percent 10；
Transparent conductive layer (112)；And
Wherein said photovoltaic device (200) has the fill factor more than 0.65.
9. the method manufacturing photovoltaic device (100), comprising:
Substrate (110) arranges transparent conductive layer；
Described transparent conductive layer (112) arranges transparent window layer (114), wherein, is being exposed to from 500 degrees Celsius to 700
Degree Celsius scope in temperature 10 minutes time, the optical property of described transparent window layer (114) is not changed more than percent
The amount of 10；
Neighbouring described transparent window layer (114) arranges the first semiconductor layer (116)；
It is provided with described transparent window layer (114) to include:
Thering is provided the target including semi-conducting material in the environment including oxygen, wherein said semi-conducting material includes cadmium and sulfur；
Described target is applied multiple direct current DC pulses to form pulse DC plasma；
With target described in described pulse DC plasma sputtering the material including cadmium and sulfur to be sprayed into described pulse DC plasma；
And
The film including described material is deposited on substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/894,242 US8044477B1 (en) | 2010-09-30 | 2010-09-30 | Photovoltaic device and method for making |
| US12/894242 | 2010-09-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102446989A CN102446989A (en) | 2012-05-09 |
| CN102446989B true CN102446989B (en) | 2016-12-14 |
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