CN101816073A - The formation method that contacts after the non-rectification in the CDTE/CDS thin-film solar cells - Google Patents

The formation method that contacts after the non-rectification in the CDTE/CDS thin-film solar cells Download PDF

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CN101816073A
CN101816073A CN200780100052A CN200780100052A CN101816073A CN 101816073 A CN101816073 A CN 101816073A CN 200780100052 A CN200780100052 A CN 200780100052A CN 200780100052 A CN200780100052 A CN 200780100052A CN 101816073 A CN101816073 A CN 101816073A
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N·罗密欧
A·波西欧
A·罗密欧
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    • H01L31/00Semiconductor 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
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Abstract

Form the method for non-rectification ohmic contact on p-N-type semiconductor N CdTe film, this method comprises the following step: deposit As under the underlayer temperature of ambient temperature to 200 ℃ on this CdTe layer 2Te 3Layer; At this As 2Te 3Deposition Cu layer on the layer; Making at least, the Cu layer of this deposition reaches 150 ℃ to 250 ℃ temperature.This method is used for forming stable back contact on the CdTe/CdS thin-film solar cells.

Description

The formation method that contacts after the non-rectification in the CDTE/CDS thin-film solar cells
Specification
Invention field
The present invention relates to technical field of solar batteries, relate more specifically to the large scale production method of CdTe/CdS thin-film solar cells.Especially, the present invention relates to this about forming the improvement of the method that contacts after the non-rectification.Although be called " CdTe/CdS film " solar cell in this manual for the sake of simplicity, it being understood that this term comprises formula Zn xCd 1-xS/CdTe yS 1-yIn all contained salt mixtures, wherein 0≤x≤0.2 and 0.95≤y≤1.
The background of invention technology
As known, the typical construction of CdTe/CdS solar cell has the film sequence that multilayer is arranged, and comprising: carrying transparent conductive oxide (TCO) film transparent glass substrate, show as the semi-conductive CdS film of n-, contact after showing as the semi-conductive CdTe film of p-and metal.Solar cell with such layer arrangement and structure is for example disclosed among the US 5304499.
Commercial float glass can be used as transparent substrates, although its cost is low, usually preferred special glass is diffused in the TCO film to avoid the shortcoming of float glass, particularly Na.
Modal TCO is the In that contains 10%Sn 2O 3(ITO).This material has about 3 * 10 -4The utmost point low-resistivity of Ω cm and the high grade of transparency in the solar spectrum visible region (>85%).But this material is by the sputter manufacturing, and the ITO target forms some tubercles that contain excessive In in the back several times in operation, and the discharge between the tubercle can take place in sputter procedure, and this may damage this film.Another kind of common used material is the SnO of doped with fluorine 2, but it shows near 10 -3The higher electric resistivity of Ω cm, therefore for realize about 10 Ω/square sheet resistance, need the layer of 1 micron thickness.So high TCO thickness reduces the transparency of solar cell and reduces photoelectric current.NREL group has also proposed to use Cd 2SnO 4(people such as X.Wu, Thin Solid Films, 286 (1996) 274-276).This material also has some shortcomings, because target is by CdO and SnO 2Mixture constitute, and CdO height moisture absorption, thus the stability of this target may be unsatisfactory.
At same Applicant WO03/032406 under one's name the method that is used for large-scale production of CdTe/CdS thin-film solar cells is disclosed, wherein with the film that can deposit utmost point low-resistivity and do not form any metal tubercle and allow to use the mode of inexpensive substrate to carry out the deposition of TCO film on target.For this reason, by at hydrogen or argon gas-hydrogen mixture and gaseous fluorine alkyls CHF for example 3Inert atmosphere in sputter, form tco layer.By this way, this TCO is mixed by fluorine.
Deposit CdS film or layer by the CdS bulk material by sputter or close-spaced sublimation (CSS).This back one technology allows to prepare film under the much higher underlayer temperature of temperature used in than simple vacuum evaporation or sputter, because substrate and evaporation source are very close each other, and apart from the 2-6 millimeter, and at inert gas such as Ar, He or N 2Exist down 10 -1Deposit under-100 millibars of pressure.Higher underlayer temperature allows growth crystalline quality better material.The key character of close-spaced sublimation is the high growth rate up to 10 microns/minute, and this is suitable for large-scale production.
On the CdS film, depositing CdTe film or layer by close-spaced sublimation (CSS) under 480-520 ℃ the underlayer temperature.Usually use the CdTe particle as the CdTe source of from open crucible, evaporating.
Usually by deposition CdTe is electrically contacted for the rear portion that the film of height p-dopant metal (as copper, in the contact of graphite for example) obtains on the CdTe film, this metal can spread in the CdTe film when annealing.Identical inventor discloses in the CdTe/CdS solar cell and has used Sb 2Te 3Film is as back contact (people such as N.Romeo, A highly efficient andstable CdTe/CdS thin film solar cell, Solar Energy Materials﹠amp; Solar Cells, 58 (1999), 209-218).
Back contact in the CdTe/Cd thin-film solar cells is realizing playing important effect aspect the described battery efficiency.Rectification contact (rectifying contact), promptly do not follow the metal-semiconductor contact (this means and between voltage and current, do not have linear relationship) of Ohm's law, in the J-V characteristic curve, promptly in the figure of the functional relation that shows current density behavior and voltage, cause " upset (roll over) " (intersection in dark condition/characteristic first quartile of illumination condition J-V), this significantly reduces " fill factor ", therefore and reduce battery efficiency (D.Bonnet and P.V.Meyers, J.Mater.Res.13 (1998) 2740-2753)).Because CdTe has high electron affinity (x) and high forbidden band (1.5eV), therefore most of metal forms Schottky barrier, limits the hole transport among this p type CdTe.When using Cu on CdTe, to form contact, before the Cu deposition, in phosphoric acid/nitric acid bath, on CdTe, carry out chemical etching (so-called N-P etching) producing rich Te surface, thereby with Cu formation Cu xTe (1≤X≤2) compound.
This compound closely contacts by diffuseing to form mutually with the low resistance of CdTe, but its stability is subject to Cu xTe phase (1≤X≤1.4), and Cu 2Te is not a stable compound mutually, therefore discharges Cu, and Cu is the rapid diffusion element, and via crystal grain edge penetration CdTe, this may cause deterioration of battery especially.Because Cu is a cation, the internal electric field of this knot is depended in its diffusion in CdTe, and this depends on that again battery stands the situation of external bias or illumination.When this device be heated above 60 ℃ temperature or stand intense light irradiation (>1sun) time, the deterioration of this device is obviously faster.
For fear of or limit this shortcoming at least, adopt the solar cell that contacts behind this type, the solar cell produced of First Solar Inc. (USA) for example, the 2 nanometer Cu thickness that use deposits after CdTe is carried out chemical etching (people such as C.R.Corwine, Sites, Sol.Energy Mat.﹠amp; Solar Cells 82 (2004) 481-489).
For fear of any deterioration of this device, disclosing novel back contact material in same Applicant WO 03/032406 patent application under one's name (is Sb 2Te 3And As 2Te 3) as the substitution material of Cu.Especially, Sb 2Te 3Be material with low band gaps (0.3eV), be the p-type and have and approach 10 -4The resistivity of Ω cm.When the underlayer temperature deposit 300 ℃ of ≈, it forms the tight efficient that also can reach near 16% that contacts with CdTe.Even such contact verified at 10-20sun the device illumination and be higher than under 100 ℃ the temperature also highly stable.Yet, although form the ohmic contact of better quality by this way, under specific CdTe film growth conditions, still to observe and in the J-V characteristic curve, have " upset ", this shows in the contact of back and has certain rectification, even be not very obvious.
Therefore, general purpose of the present invention provides and a kind ofly forms complete non-rectification and guarantee the method for the ohmic contact of membrane stability for the CdTe film.
A specific purpose of the present invention provides a kind of method of ohm back contact of the CdS/CdTe of formation thin-film solar cells, even it also can be guaranteed the stability of battery and therefore compared with prior art improve battery efficiency or battery efficiency is remained unchanged under high illumination and temperature conditions.
Another object of the present invention provides the method that contacts after the thin-film solar cells that forms the above-mentioned type, wherein, even use Cu in the formation of described back contact, the THICKNESS CONTROL of the Cu film of deposition seriously influences stability test also can be in the method for prior art.
Another object of the present invention provides the method that contacts after the thin-film solar cells that forms the above-mentioned type, wherein needn't carry out chemical etching to the CdTe film before forming the contact of described back and handle.
A further object of the present invention provides a kind of thin-film solar cells, wherein the back contact is complete non-rectification, even make and under high illumination and temperature conditions, also guarantee high stability, and compare the efficient of improving battery thus with known similar solar cell or it is remained unchanged.
Summary of the invention
Be adopted as the CdTe/CdS thin-film solar cells and form the method that contacts after the non-rectification and realized these purposes, in claim 1 and 14, set forth their essential characteristic according to the solar cell of this method.
According to an aspect of the present invention, a kind of method that forms ohmic contact is provided, this method is compared with disclosed method among the WO 03/032406, under the situation of the processing mode that does not change the CdTe film, make photovoltaic device keep stable in time, and therefore need not the etching of any kind of is carried out on CdTe film surface.
The new mode that this p-of making type CdTe obtains contacting is: deposit at first As in succession by sputter 2Te 3Film and Cu film then, but truly contact neither by As 2Te 3Provide and be not to provide by Cu, but via Cu XTe (1≤x≤1.4) compound provides.Thereby ohm behavior and time stability that this just compound is guaranteed this contact and guaranteed solar cell.
In other words, method of the present invention provides the mode that contacts behind non-rectification ohm of a kind of CdTe of formation film, comprises forming Cu thereon xTe (1≤x≤1.4) is because the reactive script between Cu and the Te can not form this Cu xTe.In fact, if adopt any method to deposit the film that contains Cu and Te, under any circumstance final result will be the separation of some phases, comprise not producing ohmic contact and because of discharging the unsettled Cu of Cu atom 2The Te phase.Stable phase between Cu and the Te is that Cu content is 1 to 1.4 phase, promptly passes through at As under the energy advantageous conditions 2Te 3Sputtering sedimentation Cu film on the film and the phase that forms, described As 2Te 3Film is deposited on the surface of the CdTe film of handling in due form.
Be suitable for being deposited on As 2Te 3Maximum Cu amount on the layer must be guaranteed good nonrectifying contact and stable system simultaneously, and therefore must allow do not staying free Cu or avoiding forming Cu 2Form Cu under the situation of Te (it can cause atom Cu to diffuse through the CdTe film and therefore cause p-n function deterioration) xTe (1≤x≤1.4).
Especially, can form Cu by natural way xTe (1≤x≤1.4) compound: or pass through under 150 ℃ to 250 ℃ temperature at As 2Te 3On carry out Cu film deposition and directly form, or pass through at low temperature (<100 ℃) deposit As 2Te 3The combination of this layer of heating forms under 150 ℃ to 250 ℃ temperature then.Particularly preferred temperature all is at least 180 ℃ in these two kinds of situations.Even needn't reach Cu xIt is last that Te (1≤x≤1.4) compound forms, and is useful but make the back contact of formation like this keep at least 1 minute under this temperature.
In the formation of back according to the present invention contact, at As 2Te 3Utilize the specific interaction between these materials in the process of last sputtering sedimentation Cu film.In this sputtering technology, the atom that arrives substrate can have tens electron-volts energy (when using thermal evaporation, it can be several electron-volts of zero points at the most).Under 200 ℃, As 2Te 3The film surface thermally labile (it begins to evaporate under 250 ℃ again) that begins to become.On the other hand, it is excessive that the Cu atom has big energy, and the excessive part of this energy is lost by surface impacts and part is used to separate As 2Te 3Thereby molecule and alternative As form more stable compound (promptly having higher formation energy), i.e. Cu under this temperature xTe (1≤x≤1.4).This stoichiometric proportion is variable (X is variable between 1 and 1.4), because the hydridization of chemical bond may take place, this may cause the formation energy that increases progressively from x=1.4 to x=1.
Shown in x-ray diffraction pattern, As 2Te 3Stop Cu, if because itself and Cu reaction and Cu film remain on the value that is not more than 20 nanometers, then form stabilizing material, promptly x is 1 to 1.4 Cu xTe, it forms the nonrectifying contact (seeing Fig. 3 and 4) with CdTe.
Observe, if use Sb 2Te 3Replace As 2Te 3, can't realize identical result, because Sb 2Te 3Highly stable and not with Cu reaction, therefore Cu can diffuse through Sb in the CdTe layer 2Te 3Film destroys this device thus.
The accompanying drawing summary
Now with reference to accompanying drawing the present invention is described in more detail, wherein:
Fig. 1 schematically illustrates the structure of the CdTe/CdS thin-film solar cells with back of the present invention contact;
Fig. 2 has shown the method according to this invention but the J-V characteristic curve of two solar cells contacting after two kinds of different deposition temperatures deposit (that is: ambient temperature, curve a; 200 ℃, curve b);
Fig. 3 is at As on glass 200 ℃ of underlayer temperature deposit 2Te 3The x-ray analysis of film, this As 2Te 3Film has (curve b) and does not have that (curve is a) at uniform temp deposit 20 nanometer Cu layers thereon;
Fig. 4 is at As on glass 200 ℃ of underlayer temperature deposit 2Te 3The x-ray analysis of film, this As 2Te 3Film has (curve b) and does not have that (curve is a) at uniform temp deposit 50 nanometer Cu layers thereon.
Detailed Description Of The Invention
Has this new A s according to the inventive method 2Te 3The peculiar key step of production of the CdTe/CdS thin-film solar cells that contacts behind+the Cu is:
A. cleaning glass is with the organic residue (grease, solvent etc.) of removing any trace and particulate (size greater than 1 micron dust).
B. by sputtering at the transparent preceding contact of deposition on glass, described contact comprises two-layer: ground floor is the ITO (indium tin oxide) that guarantees conductivity, the second layer is ZnO, and this ZnO serves as resilient coating or serves as the barrier layer that may spread of impurity in the layer that prevents from will deposit in the subsequent step.This is two-layer must guarantee to be not less than 85% transparency on the whole in visible wavelength range.
C. pass through reactive sputtering (RF-magnetron) at Ar+%5CHF3 environment deposit CdS film, this CdS provides the n-N-type semiconductor N of the first of this knot.
D. by CSS (close-spaced sublimation) deposition CdTe film.This CdTe is the p-N-type semiconductor N, the absorption fully that it provides the second portion of this knot and guarantees visible light.
E. the combining structure of whole previous preparation is being heat-treated under 400 ℃: make CdTe film surface in the atmosphere of Ar+ freon, expose no more than 5 minutes, temperature was kept other 5 minutes at 400 ℃, set up vacuum condition, the volatile compound that forms during the first is evaporated from this CdTe film surface again.
F. deposit the back contact by sputter, back according to the present invention contact comprises two-layer: ground floor As 2Te 3, and second layer Cu: subsequently on back contact that so forms deposition Mo film to guarantee suitable sheet resistance.
The schematic structure of the solar cell of so making is presented among Fig. 1.
On the CdTe surface, directly deposit As 2Te 3Layer does not carry out any chemical etching to this CdTe surface, and at about 200 ℃, preferred 180 ℃ underlayer temperature deposit Cu layer.As 2Te 3Be that the forbidden band is that 0.6eV and resistivity are about 10 -3The p-N-type semiconductor N of Ω cm.As 2Te 3Thickness can not wait for 100 to 300 nanometers, and Cu thickness can not wait for 2 to 20 nanometers.In experimental test, As 2Te 3All pass through sputtering sedimentation with Cu, the former with 10 to
Figure GPA00001009740300071
Deposition rate deposition, the latter with
Figure GPA00001009740300072
Deposition rate deposition.
If As 2Te 3All deposit at ambient temperature under without any heat treated situation with Cu, the result produces as from the visible rectification contact of the curve a of Fig. 2, wherein can see " upset " (bending of J-V curve) in this J-V characteristic curve first quartile.If at about 200 ℃ underlayer temperature deposit Cu, then should upset disappear (the curve b of Fig. 2), and the fill factor of this device high in this case (0.7, but not 0.57 in first kind of situation).
In order to understand this As 2Te 3The behavior of+Cu bilayer is by directly at deposition on glass As 2Te 3+ Cu prepares some samples and at about 200 ℃ underlayer temperature deposit Cu.In addition, by at As 2Te 3The Cu thickness of maximum 20 nanometers of last deposition prepares some samples, and prepares other samples by the Cu layer that deposits about 50 nanometers.To these samples carry out the x-ray analysis and with only contain As 2Te 3Sample compare.According to observations, contain the sample that layer thickness is not more than the Cu of 20 nanometers and show several Cu of 1≤X≤1.4 xTe phase (Fig. 3, curve a and b), and contain layer thickness be 50 nanometers Cu sample in addition show Cu 2Te phase (Fig. 4, curve a and b).The result of above-mentioned test is, thereby the Cu layer that can deposit maximum 20 nanometer thickness forms Cu xTe phase (1≤X≤1.4), it forms the stable nonrectifying contact with CdTe.CdTe/CdS battery J-V characteristic curve-curve b shown in Fig. 2 has also confirmed this point, in this battery, by deposit the As of 200 nanometers in succession under about 200 ℃ underlayer temperature 2Te 3With contact after the Cu of 20 nanometers makes, and any etching is not carried out on this CdTe surface.The fill factor of this battery is~0.7.
Can reach a conclusion As by these data 2Te 3The barrier layer of serving as Cu, and when depositing Cu at a lower temperature and after deposition, making it reach about 200 ℃, at As 2Te 3And solid-state reaction takes place between the Cu, thereby wherein Cu displacement As forms Cu xThe Te phase.
The mode that forms nonrectifying contact on p-type CdTe seems to be similar to mode commonly used, wherein at first produces the surface of rich Te by the chemical etching of CdTe, deposits Cu then to form Cu xTe.Yet marked difference is, does not carry out any CdTe etching in the method for the invention, and is to use the Cu amount up to 10 times.This makes the risk that forms the rectification contact more inessential, thereby allows this contact to have bigger stability.
For assess performance and photovoltaic parameter, according to the As of method of the present invention by different-thickness listed in the sputtering sedimentation following table in succession 2Te 3Prepare several solar cell samples with Cu:
Sample ??As 2Te 3Nanometer The Cu nanometer Underlayer temperature, ℃
??1 ??100 ??20 ??200
??2 ??300 ??5 ??200
??3 ??200 ??10 ??<100
Under the situation of sample 3, make the system that forms by all sedimentary deposits in Ar atmosphere, be issued to 180 ℃ to 250 ℃ underlayer temperature at 100 millibars of pressure to 1atm.In all samples, by at this As 2Te 3The Mo layer of deposition 150nm is finished this contact on the+Cu film surface.When speed is several Extremely
Figure GPA00001009740300082
And when underlayer temperature is 150 ℃ to 250 ℃, do not observe the physics relevant difference of the touching act that depends on deposition rate.
Under all these situations, this back contact is verified to be excellent contact for the CdTe/Cds thin-film solar cells, shown in J-V characteristic curve (Fig. 2, curve b).In fact, in this characteristic positive part (first quartile), show crookedly, this confirms that this contact is non-rectification, and can be derived by the slope of curve and fill factor and not have any series resistance effect.Therefore, this contact be non-rectification and have a low resistance.By under open-circuit condition, making this device stand " light is saturated ", promptly, carry out stability test exposing 8 hours up to the strong illumination of 10sun with under up to 100 ℃ temperature, do not notice the remarkable variation of the photovoltaic parameter of this device.
Although As 2Te 3With this two-layer preferred deposition technique of Cu be by sputter, yet they also can be by thermal evaporation, by electron gun evaporation or electrodeposition process deposition.
Can be under not deviating from make and change and/or revise to the formation method of the non-rectification ohmic contact that is used for the CdTe/CdS film with to thin-film solar cells of the present invention as the situation of following claims of the present invention scope.

Claims (16)

1. on p-N-type semiconductor N CdTe film, form the method for non-rectification ohmic contact, it is characterized in that this method comprises the following step:
A) under the underlayer temperature of ambient temperature to 200 ℃, on described CdTe layer, deposit As 2Te 3Layer,
B) at described As 2Te 3Deposition Cu layer on the layer,
C) making at least, the Cu layer of this deposition reaches 150 ℃ to 250 ℃ temperature.
2. according to the process of claim 1 wherein that the thickness of Cu layer of this deposition is not more than 20 nanometers.
3. according to the method for claim 1 or 2, wherein under 150 to 250 ℃ temperature, carry out the deposition of this Cu layer.
4. according to the method for claim 1 or 2, wherein, make this layer combination reach 150 ℃ to 250 ℃ temperature then being lower than the deposition of carrying out the Cu layer under 100 ℃ the temperature.
5. according to the method for claim 4, wherein carry out heating under 150 ℃ to 250 ℃ temperature to the 1 atmospheric pressure Ar atmosphere and 100 millibars.
6. according to the method for claim 4 or 5, wherein this layer is combined under 150 ℃ to 250 ℃ the temperature and kept at least 1 minute.
7. according to each method in the aforementioned claim, As that wherein should deposition 2Te 3The thickness of layer is 100 to 300 nanometers.
8. according to each method in the aforementioned claim, wherein said contact is the back contact of CdTe/CdS thin-film solar cells.
9. according to each method in the aforementioned claim, wherein do not standing to deposit As on the CdTe layer that any chemical etching handles 2Te 3Layer.
10. according to each method in the aforementioned claim, deposition Mo layer on this Cu layer wherein.
11. according to each method in the aforementioned claim, wherein by sputtering sedimentation As 2Te 3Layer, Cu layer and Mo layer.
12. according to each method in the claim 1 to 10, wherein by thermal evaporation, electron gun evaporation, electrodeposition process deposition As 2Te 3Layer, Cu layer and Mo layer.
13. according to each method in the aforementioned claim, wherein said ohmic contact is by the Cu of 1≤X≤1.4 xTe forms.
14. the CdTe/CdS thin-film solar cells that forms by sandwich construction, this sandwich construction comprises transparent substrates, be deposited on conductive oxide layer on the described substrate, n-type CdS semiconductor layer, p-type CdTe semiconductor layer, at least one contains the back contact of Cu, it is characterized in that it further comprises the As that is deposited on the described CdTe semiconductor layer 2Te 3The layer and at described As 2Te 3The Cu of middle 1≤X≤1.4 that form xThe Te layer.
15. according to the solar cell of claim 14, wherein the thickness of the Cu layer of this deposition is not more than 20 nanometers.
16., wherein be somebody's turn to do the As of deposition according to the solar cell of claim 14 or 15 2Te 3Layer thickness is 100 to 300 nanometers.
CN2007801000524A 2007-06-28 2007-06-28 Method for the formation of a non-rectifying back-contact in a CDTE /CDS thin film solar cell Expired - Fee Related CN101816073B (en)

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ITLU20050002A1 (en) * 2005-02-08 2006-08-09 Solar Systems & Equipments Srl A NEW PROCESS FOR THE TREATMENT IN CHLORINE ENVIRONMENT OF SOLID FILM CELLS OF CdTe / CdS without the use of CdC12.

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