CN101924162A - Method for preparing copper-indium-gallium-selenium compound membrane - Google Patents
Method for preparing copper-indium-gallium-selenium compound membrane Download PDFInfo
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- CN101924162A CN101924162A CN2009101491404A CN200910149140A CN101924162A CN 101924162 A CN101924162 A CN 101924162A CN 2009101491404 A CN2009101491404 A CN 2009101491404A CN 200910149140 A CN200910149140 A CN 200910149140A CN 101924162 A CN101924162 A CN 101924162A
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Abstract
The invention relates to a method for preparing a copper-indium-gallium-selenium compound membrane. The method comprises the following steps of: providing a substrate; forming an adhesive coating on the substrate; forming a metal electrode layer on the adhesive coating; forming a precursor stack membrane layer on the metal electrode layer, wherein the precursor stack membrane layer comprises a plurality of copper-gallium alloy layers and at least one copper-indium alloy layer clamped among the copper-gallium alloy layers; performing a tempering process to transform the precursor stack membrane layer into a copper-indium-gallium alloy layer; and performing a selenylation process to transform the copper-indium-gallium alloy layer into a copper-indium-gallium-selenium compound layer.
Description
Technical field
The invention relates to the making of compound semiconductor film, and particularly about a kind of Copper Indium Gallium Selenide (Copper Indium Gallium Diselenide, the CIGS) manufacture method of compound film.
Background technology
Solar cell is a main flow with the Silicon Wafer solar cell mainly at present.Yet because the making of Silicon Wafer solar cell needs factory building in large scale and expend a large amount of energy, so its material cost and cost of manufacture are still high.And based on the restriction of physical property, the thickness of Silicon Wafer solar cell is not less than 200 μ m usually at present, therefore needs to use quite a lot of silicon raw material.
Therefore, just develop numerous other type solar cells manufacturing technologies that to be different from the Silicon Wafer solar cell in recent years, one of them is for adopting Copper Indium Gallium Selenide (Copper Indium Gallium Diselenide, IB-IIIA-VIA CIGS)
2The thin-film solar cells of compound-material (thin film solar cell), its applied chemistry formula is CuInGaSe
2The extinction spectrum scope of Copper Indium Gallium Selenide (CIGS) compound film extremely wide and have goodish stability, thereby can be used as the usefulness of the absorbed layer (absorber) in the thin-film solar cells.By application as above-mentioned copper-indium-gallium-selenium compound membrane, thin-film solar cells can adopt material substrates such as glass, plastics or the stainless steel of relative low price and prepare, its thickness can more reduce than traditional silicon wafer solar cell, thereby helps application such as a large amount of productions of solar cell and large tracts of land production.
After the main employing sputter program of copper-indium-gallium-selenium compound membrane will comprise that a plurality of precursors retes of materials such as metal, alloy and compound are formed on the substrate at present, then re-use the predecessor rete of these sputters of selenizing routine processes on substrate, so as to finishing the making of copper-indium-gallium-selenium compound membrane.
Please refer to Fig. 1-2, shown a kind of manufacture method of known copper-indium-gallium-selenium compound membrane.
As shown in Figure 1, at first providing a substrate 100, for example is the substrate of materials such as glass, metal forming and macromolecular material.Be formed with a molybdenum layer 102 on substrate 100, its thickness is approximately between 500～1200nm.Then on molybdenum layer 102, then adopt sputter program (not shown) and form a bronze medal gallium alloy layer 104, an indium metal layer 106 and another copper gallium alloy layer 108 in regular turn.The copper gallium alloy layer 104, the indium metal layer 106 that are stacked on the molybdenum layer 102 are as a precursors structure 110 for preparing the copper-indium-gallium-selenium compound semiconductive thin film with copper gallium alloy layer 108.
Please refer to Fig. 2, then a tempering program (not shown) and a selenizing program 112 in regular turn, above-mentioned copper gallium alloy layer 104, indium metal layer 106 and copper gallium alloy layer 108 alloying and selenizing formed (chalcopyrite) structure that has chalcopyrite and copper-indium-gallium-selenium compound membrane 114.
The precursors structure of the copper-indium-gallium-selenium compound semiconductive thin film of employing shown in Fig. 1-2 and formed copper-indium-gallium-selenium compound membrane 114 have shortcomings such as the not good and thickness evenness of film evenness is inconsistent.Its reason is that the fusing point of the indium metal in the indium metal layer 106 is 156.6 ℃, and the sputter temperature when adopting the sputter program to form indium metal layer 106 is usually approximately between 150～250 ℃ and be higher than the fusing point of indium metal, so indium metal was to form with melting attitude or half melting state when sputter formed indium metal layer 106 on copper gallium alloy layer 104, thereby in the indium metal film on copper gallium alloy layer 104 surface, produce graininess pile up with and make indium metal layer 106 produce irregular surface and uneven thickness, as shown in Figure 1.And the indium metal layer 106 with out-of-flatness surface and uneven gauge also influences the deposition situation of the predecessor structure 110 that comprises copper gallium alloy layer 104, indium metal layer 106 and copper gallium alloy layer 108, and has produced the copper-indium-gallium-selenium compound membrane 114 that also has the out-of-flatness surface after selenizing program 112 is implemented.Have out-of-flatness like this surface and will have influence on the battery efficiency of its applied thin-film solar cells, and reduce the thin-film solar cell photoelectric conversion efficiency with the copper-indium-gallium-selenium compound membrane 114 of uneven gauge.
In addition, structure as shown in Figure 2 also has following problem.Promptly when implementing selenizing program 112 as structure shown in Fig. 1, the rete peeling phenomenon often appears in formed copper-indium-gallium-selenium compound membrane 114, and this rete peeling phenomenon often betides molybdenum electrode layer 102 and substrate 100 at the interface.Shown that so copper-indium-gallium-selenium compound membrane 114 makes molybdenum layer 102 and substrate 100 produce segregation phenomenons in the execution of selenizing program often because of thermal stress is excessive.It is interior as material coefficient of thermal expansion differences at high temperature such as glass, metal forming and macromolecules with substrate 100 that above-mentioned thermal stress mainly comes from molybdenum layer 102.Because the thermal coefficient of expansion that the thermal coefficient of expansion of substrate 100 applied materials and molybdenum layer are 102 has difference; so in the process temperatures more than 400 ℃; regular meeting occurs based on the big stress difference phenomenon that thermal dilation difference caused, and this phenomenon also is to cause to betide the reason that copper-indium-gallium-selenium compound membrane 114/ molybdenum electrode layer 102 and 100 retes of substrate peel off.
Summary of the invention
In view of this, the invention provides the manufacture method of copper-indium-gallium-selenium compound membrane, to solve above-mentioned known problem.
According to an embodiment, the invention provides a kind of manufacture method of copper-indium-gallium-selenium compound membrane, comprising: a substrate is provided; Form an adhesion coating on this substrate; Form a metal electrode layer on this adhesion coating; Form a predecessor and pile up rete on this metal electrode layer, wherein this predecessor piles up rete and comprises a plurality of copper gallium alloy layers and be folded at least one copper and indium alloy layer between those copper gallium alloy layers; Implement a tempering program, to pile up rete be a bronze medal indium gallium alloy layer to transform this predecessor; And implement a selenizing program, be a copper-indium-gallium-selenium compound layer to transform this copper indium gallium alloy layer.
The present invention can improve the surface roughness of resulting copper gallium indium selenium compound film, and improves its battery efficiency and photoelectric conversion efficiency when thin-film solar cell applications.
For above and other objects of the present invention, feature and advantage can be become apparent, a preferred embodiment cited below particularly, and cooperate appended accompanying drawing, be described in detail below:
Description of drawings
Fig. 1-2 has shown the manufacture method of known copper-indium-gallium-selenium compound semiconductive thin film;
Fig. 3-5 has shown the manufacture method according to the copper-indium-gallium-selenium compound semiconductive thin film of one embodiment of the invention;
Fig. 6-7 has shown the manufacture method according to the copper-indium-gallium-selenium compound semiconductive thin film of another embodiment of the present invention;
Fig. 8 is a flow chart, has shown the manufacture method according to the copper-indium-gallium-selenium compound semiconductive thin film of one embodiment of the invention;
Fig. 9 is a spectrogram, has shown the X-ray diffraction analysis result according to the resulting copper-indium-gallium-selenium compound membrane of one embodiment of the invention.
[primary clustering symbol description]
100～substrate; 102～molybdenum layer;
104,108～copper gallium alloy layer; 106～copper gallium alloy layer;
110～precursors structure; 112～selenizing program;
114～copper-indium-gallium-selenium compound membrane; 200～substrate;
202～adhesion coating; 204～metal electrode layer;
206,210～copper gallium alloy layer; 208～copper and indium alloy layer;
212～predecessor piles up rete; 214～tempering program;
216～copper indium gallium alloy layer; 218～selenizing program;
220～copper-indium-gallium-selenium compound layer; 300～substrate;
302～adhesion coating; 304～metal electrode layer;
306,310,314～copper gallium alloy layer; 308,312～copper gallium alloy layer;
316～predecessor piles up rete; 320～copper gallium alloy layer.
Embodiment
Embodiments of the invention will be by hereinafter and cooperate accompanying drawings such as Fig. 3-9 to do an explanation.
Please refer to Fig. 3-5, shown manufacture method according to the copper-indium-gallium-selenium compound membrane of one embodiment of the invention.
As shown in Figure 3, at first providing a substrate 200, for example is the substrate of materials such as glass, metal forming and macromolecular material.At this, substrate 200 is gone up remaining as filths such as oil stain or microparticles for through cleaning clean substrate to remove its surface.Then on substrate 200, form an adhesion coating 202 and a metal electrode layer 204 in regular turn.Adhesion coating 202 is used to improve the thermal expansion coefficient difference of 200 of metal electrode layer 204 and substrates and strengthens the situation of adhering between metal electrode layer 204 and substrate.In one embodiment, adhesion coating 202 for example is being higher than a molybdenum layer that forms under the pressure of 5mtorr on the metal electrode layer 204 for the employing method for sputtering, and metal electrode layer 204 is for example for adopting method for sputtering in the following molybdenum layer that is formed on the adhesion coating 202 of a pressure that is lower than 5mtorr.In the present embodiment, be preferably between under the pressure of 6～8mtorr and form a molybdenum layer on the metal electrode layer 204 as the molybdenum layer of adhesion coating 202.In one embodiment, the thickness of adhesion coating 202 is approximately between 50～600 nanometers, and the thickness of metal electrode layer 204 is approximately between 200～600nm, and adhesion coating 202 and 204 of metal electrode layers have and be not more than one of 1200 nanometers and combine thickness, for example are a thickness of about 1000 nanometers.In other embodiments, a but metal level of adhesion coating 202 titaniferous, tantalum, cobalt, chromium, nickel, tungsten or its alloys, so as to the thermal expansion coefficient difference of 200 of the metal electrode layer that improves follow-up formation and substrates, metal electrode layer then can be a metal level that contains molybdenum.
Then, form a predecessor and pile up rete 212 on the surface of metal electrode layer 204, it comprises two bronze medal gallium alloy layers 206 and 210 and the copper and indium alloy layer 208 that is folded in these copper gallium alloy layers 206 and 210.At this, predecessor pile up in the rete 212 copper gallium alloy layer 206 and 210 and copper and indium alloy layer 208 can adopt as the combination of method such as sputter, evaporation, plating or said method and be formed on the metal electrode layer 204.In one embodiment, pile up copper gallium alloy layer 206 and 210 and during copper and indium alloy layer 208 in the rete 212, can adopt Cu when adopting method for sputtering to form predecessor
yGa
1-yWith Cu
xIn
1-xDeng the material source of target as these a little retes, Cu wherein
yGa
1-yGallium content in the alloy target material needs less than 78% (y＞0.22) and Cu
xIn
1-xCopper content need be higher than 4% (x＞0.04) in the target, can keep target and the alloy rete of sputter on metal electrode layer 204 solid-state in the sputter program, and the thickness that piles up rete in order to predecessor distributes average with composition.Therefore in the present embodiment, the copper gallium alloy layer 206 and 210 that adopts the resulting predecessor of method for sputtering to pile up in the rete 212 will have a chemical formula Cu
yGa
1-y, 0.22＜y＜0.9 wherein, copper and indium alloy layer 208 then has a chemical formula Cu in it
xIn
1-x, 0.04＜x＜0.5 wherein.In another embodiment, copper gallium alloy layer 206 and 210 has a thickness copper and indium alloy layer 208 between 100～600nm and then has a thickness between 200～700nm.It is interior under the different thickness degree of depth that predecessor as shown in Figure 3 piles up rete 212, each metallic element distributes and proportion of composing can be finely tuned slightly, after containing the selenium compound film with the generation of selenium element reaction, the element distribution of the different thickness degree of depth will no longer be that single composition distributes along with Thickness Variation in the feasible compound film that is generated, and this result helps to obtain best compound film.
Please refer to Fig. 4, then implement a tempering program 214, transform into a bronze medal indium gallium alloy layer 216 predecessor is piled up rete at structure shown in Figure 3.In one embodiment, tempering program 214 is to implement about 10-80 minute under a temperature of 150 ℃～400 ℃.The execution temperature of tempering program in another embodiment, 214 preferably is about 300 ℃ and preferably implemented about 40 minutes.Implementing the resulting bronze medal indium gallium alloy layer 216 in back in tempering program 214 also has smooth and membrane structure uniform film thickness, and the copper in copper indium gallium alloy layer has the element ratio between 0.6～1.3, and the gallium element in the copper indium gallium alloy layer is between 0.1～0.5 element ratio, with the quality of the copper-indium-gallium-selenium compound membrane of guaranteeing follow-up formation.
Please refer to Fig. 5, then implement a selenizing program 218, so that copper indium gallium alloy layer 216 is transformed into a copper-indium-gallium-selenium compound layer 220 at structure shown in Figure 4.In one embodiment, selenizing program 216 is under a temperature of 450 ℃～600 ℃ and between 1*10
-6The pressure of torr～10mtorr was implemented about 10-100 minute down.Implementing the resulting copper-indium-gallium-selenium compound layer 220 in back in selenizing program 216 also has smooth and membrane structure uniform film thickness.Can adopt in the above-mentioned selenizing program 216 selenium steam or through plasma dissociate obtain as Se
+And Se
++Ionic state selenium and copper indium gallium alloy layer 216 (see figure 4) react, and then obtain copper-indium-gallium-selenium compound layer 220.
As shown in Figure 5, be formed at that copper-indium-gallium-selenium compound layer 220 on the metal electrode layer 204 has flat surface this moment and its thickness is quite even.At this, because copper-indium-gallium-selenium compound layer 220 is the quaternary compound material, so on its thickness direction, gallium, phosphide element present composition different and heterogeneous and distribute, but on copper-indium-gallium-selenium compound layer 220 surface composition distributed, gallium, phosphide element then can present the uniformity of high level.
So, because the copper-indium-gallium-selenium compound layer 220 shown in Fig. 5 has homogeneous film thickness, thereby have the distribution of uniform face composition, and can after the selenizing program, produce the copper-indium-gallium-selenium compound membrane of uniform film thickness.In the present embodiment rete that piles up that rete substitutes known copper gallium alloy layer, indium metal layer and copper gallium alloy layer that piles up that adopts copper gallium alloy layer 206, copper and indium alloy layer 208 and copper gallium alloy layer 210, so can improve the predecessor film shortcoming of known sputter process made and promote the efficient of the compound film solar cell that made finishes.
Please refer to Fig. 6-7, shown manufacture method according to the copper-indium-gallium-selenium compound membrane of another embodiment of the present invention.Present embodiment is to be obtained by the embodiment that revises Fig. 3-5, only describes its different place at this.
As shown in Figure 6, at first provide a substrate 300.Then on substrate 300, form an adhesion coating 302 and a metal electrode layer 304 in regular turn.Then, form a predecessor and pile up rete 316 on the surface of metal electrode layer 304, it comprises three copper gallium alloy layers 306,310 and 314 and two copper and indium alloy layers 308 and 312 of being folded in 306,310 and 314 on these copper gallium alloy layers respectively.
Please refer to Fig. 7, then implement a tempering program and a selenizing program (all demonstration) to form a copper-indium-gallium-selenium compound layer 320 at structure shown in Figure 6.
In the present embodiment, employed substrate 300, adhesion coating 302 and the relevant enforcement situation of metal electrode layer 304 all are same as substrate 200, the adhesion coating 202 and metal electrode layer 204 in the previous embodiment.In addition, predecessor in the present embodiment piles up the composition of rete 316 then than having had more two copper gallium alloy layers and a copper and indium alloy layer in the previous embodiment respectively, these copper gallium alloy layers 306,310 with 314 and the relevant enforcement situation of copper and indium alloy layer 308 and 312 all be same as copper and indium alloy layer 206 and 210 and copper and indium alloy layer 208 in the previous embodiment, then no longer be repeated in this description it at this and implement situation.
Please refer to Fig. 7, in the present embodiment, be formed at that copper-indium-gallium-selenium compound layer 320 on the metal electrode layer 304 has flat surface this moment and its thickness is quite even.At this, because copper-indium-gallium-selenium compound layer 320 is the quaternary compound material, so on its thickness direction, gallium, phosphide element present composition different and heterogeneous and distribute, but on copper-indium-gallium-selenium compound layer 320 surface composition distributed, gallium, phosphide element then can present the uniformity of high level.So, because the copper-indium-gallium-selenium compound layer 320 shown in Fig. 7 has homogeneous film thickness, thereby have the distribution of uniform face composition, and can after the selenizing program, produce the copper-indium-gallium-selenium compound membrane of uniform film thickness.Be to adopt three copper gallium alloy layers 306,310 and 314 and be folded in two copper and indium alloy layers 308 of 306,310 and 314 on these copper gallium alloy layers and 312 the rete that piles up that piles up rete alternative known copper gallium alloy layer, indium metal layer and copper gallium alloy layer respectively in the present embodiment, so can improve the predecessor film shortcoming of known sputter process made and promote the efficient of the compound film solar cell that made finishes.
Fig. 8 is a flow chart, has shown the manufacture method according to the copper-indium-gallium-selenium compound semiconductive thin film of one embodiment of the invention, and it has disclosed the manufacturing process with Fig. 6-7 illustrated embodiment as Fig. 3-5.
Please refer to Fig. 8, a substrate is provided in step S801.This substrate is the substrate through cleaning, with remove substrate surface remaining oil stain and microparticle.The mode of cleaning base plate can utilize cleaning agent to add that vibration of ultrasonic wave strengthens cleaning performance, finishes whole cleaning process with drying procedure at last again based on the wet-cleaned method.Then, in step S803, then carry out the deposition of metal electrode layer, it is to insert in the deposition chamber through the substrate that cleans, and adopts as the combination of method such as sputter, evaporation, plating or said method deposition formation one adhesion coating and a metal electrode layer in regular turn on substrate.Then, in step S805, then on metal electrode layer, adopt the method for sputter, evaporation, plating or its combination to form a predecessor and pile up rete, this predecessor piles up rete and comprises several copper gallium alloy layers and be folded at least one copper and indium alloy layer between these a little copper gallium alloy layers, and predecessor piled up rete and had a flat surfaces and have a uniform thickness this moment.Then, implement a tempering program in step S807, the predecessor that this has been comprised several copper gallium alloy layers and at least one copper and indium alloy layer piles up rete and is converted into a bronze medal indium gallium alloy layer.Then, in step S807, implement a selenizing program, so that resulting copper indium gallium alloy layer is converted into a copper-indium-gallium-selenium compound layer, shown in step S811.
Embodiment:
Embodiment 1:
One glass substrate is placed in the glass cleaner, utilize the ultrasonic oscillation device to quicken the cleaning glass effect again, subsequently glass is put into deionized water (DI water), and with DI water flushing until glass do not have cleaning solution residual till, then, glass is put into baking oven dry glass under 150 ℃ temperature, the glass substrate that cleaning is finished is inserted in the sputter machine vacuum cavity immediately, extracts air and makes the vacuum cavity atmospheric pressure value be lower than 1x10 with vacuum pump
-6Torr, after the vacuum cavity force value reaches background pressure, feeding flow is the argon gas of 10sccm, sputter chamber vacuum value is gone up to 10mtorr, and utilize the DC sputtering method, first molybdenum film of sputter one layer thickness 400nm under the pressure of 10mtorr this moment, at this first molybdenum film and glass substrate preferable tack is arranged, so first molybdenum film is as an adhesion coating, yet this first molybdenum film conductivity is relatively poor, and the sheet resistor value often is higher than 1ohms/square.Then, improve pumping efficiency with the vacuum values of keeping the sputter cavity at 2mtorr, utilize the DC sputtering way again, sputter one second molybdenum film above first molybdenum film, this second molybdenum film thickness is 600nm, and second molybdenum film and glass substrate tack are relatively poor, therefore can't use as adhesion coating.Change the molybdenum film oxygen content of may command institute sputter by sputter pressure, to regulate the rerum natura of first and second molybdenum film, under higher operating pressure, can obtain the higher and preferable molybdenum film of tack of oxygen content, the lower molybdenum film of the next formation oxygen content of lower operating pressure, and have preferable conductivity (＜0.2ohms/square).Finish the molybdenum film/glass substrate structure of making and still stay in the sputter cavity, make Cu as shown in Figure 6 with the DC sputtering way again
yGa
1-y/ Cu
xIn
1-x/ Cu
yGa
1-y/ Cu
xIn
1-x/ Cu
yGa
1-yPile up rete.It is to utilize Cu
0.73Ga
0.27With Cu
0.48In
0.52Alloy target material is a precursor material, earlier on molybdenum film/glass substrate structure substrate with the Cu of 160W power sputter one deck 100nm
0.73Ga
0.27Alloy firm reduces power subsequently to 60W, and the Cu of sputter one deck 400nm
0.48In
0.52Alloy firm is in Cu
0.73Ga
0.27The alloy firm surface, the Cu that follows at sputter one deck 100nm
0.73Ga
0.27The Cu of alloy firm and 400nm
0.48In
0.52Alloy firm, the last Cu of sputter one deck 150nm again
0.73Ga
0.27Alloy firm, these five layers alloy firm that piles up alternately constitute Cu
0.48In
0.52/ Cu
0.73Ga
0.27Stacked structures is for making the predecessor of copper-indium-gallium-selenium compound layer.Five layers that complete are piled up Cu alternately
0.48In
0.52/ Cu
0.73Ga
0.27Structure can obtain the Cu of uniform film thickness
0.48In
0.52/ Cu
0.73Ga
0.27Predecessor piles up rete, and its thickness is about about 1150nm.Subsequently with these five layers of Cu that piles up alternately
0.48In
0.52/ Cu
0.73Ga
0.27Pile up rete and take out, and move into immediately in the selenizing stove, then feed the argon gas of 150cc/min, this inert gas shielding is piled up Cu for five layers alternately
0.48In
0.52/ Cu
0.73Ga
0.27It is not oxidized that predecessor piles up rete, and with 40 ℃/min programming rate to Cu
0.48In
0.52/ Cu
0.73Ga
0.27Predecessor piles up the rete heating, when temperature arrives 400 ℃, holds warm 60min, changes into copper gallium indium alloy-layer so as to predecessor being piled up rete.Then again with the programming rate heating copper gallium indium alloy-layer to 550 of 15 ℃/min ℃, and hold warm 60min, when carrying out above-mentioned intensification, be same as and produce selenium steam in the selenizing stove and keep selenium steam more than supersaturated vapor is pressed, and then implement the selenizing program and with copper gallium indium alloy-layer and selenium element reaction and transform into copper gallium indium selenium compound layer at copper gallium indium alloy-layer.This copper gallium indium selenium compound layer at the selenizing descent of temperature, can be finished the making of copper gallium indium selenium compound layer after formation.
Then with this copper gallium indium selenium compound layer with X-ray diffraction analysis (XRD) after, can obtain as shown in Figure 9 spectrogram and coherent element analysis result.As shown in Figure 9, formed copper gallium indium selenium compound layer has highly crystalline and belongs to polycrystalline structure, and it has (112), (220/204), (312/116), (400/008) and (332/316) crystal plane, represents this method can produce CuIn
1-xGa
xSe
2Film, particularly the preferred crystalline phase of (112) face also produces, and therefore, the present invention can utilize a Cu
0.48In
0.52/ Cu
0.73Ga
0.27Predecessor piles up rete and obtain copper gallium indium selenium compound layer after selenizing, and this CIGS thin-film is the polycrystalline phase, shows that by the result of XRD analysis crystallinity is good, can use as the absorbed layer of copper gallium indium selenium compound thin-film solar cells.
Embodiment 2:
Glass substrate is inserted in the glass cleaner, and utilize ultrasonic oscillation device reinforced glass cleaning effect, glass substrate after the cleaning, put into deionized water (DI water) immediately, and with DI water flushing until glass do not have cleaning solution residual till, then, glass is put into baking oven under 150 ℃ temperature, dry glass, the glass substrate that cleaning is finished is inserted in the sputter machine vacuum cavity again, extracts air with pumping, makes the vacuum cavity atmospheric pressure value be lower than 1x10
-6Torr, after the vacuum cavity force value reaches background pressure, feeding flow is the argon gas of 10sccm, sputter chamber vacuum value is gone up to 2mtorr, and keep the sputter chamber vacuum, utilize the DC sputtering method this moment at 2mtorr, with the titanium sputter in glass baseplate surface, titanium is 100nm because of belonging to film thickness, and this layer titanium is adhesion coating, because of titanium and glass have preferable tack; Carry out molybdenum film subsequently and make under the 2mtorr operating pressure, molybdenum film thickness is 800nm, and this moment, molybdenum film sheet resistor value was lower than 0.2ohms/square.Make platinum/titanium metal thin film when the glass substrate with sputtering method, because of back extended meeting sputter one molybdenum film and Cu again
yGa
1-y/ Cu
xIn
1-x/ Cu
yGa
1-yStacked structures, so in order to keep the stability between titanium and glass, titanium thickness should be greater than 50nm, Zui Jia thickness is 100nm in this embodiment.To titanium similar merit able one is arranged in addition, also have Ta, Cr, Co, Ni, metal such as W or its alloy all are with glass preferable tack to be arranged, can be as the adhesion coating of glass substrate and Mo electrode.Finish the titanium and the molybdenum film/glass substrate structure of making and still stay in the sputter cavity, make Cu as shown in Figure 6 with the DC sputtering way again
yGa
1-y/ Cu
xIn
1-x/ Cu
yGa
1-y/ Cu
xIn
1-x/ Cu
yGa
1-yPile up rete.It is to utilize Cu
0.73Ga
0.27With Cu
0.48In
0.52Alloy target material is a precursor material, earlier on titanium and molybdenum film/glass substrate structure substrate with the Cu of 160W power sputter one deck 100nm
0.73Ga
0.27Alloy firm reduces power subsequently to 60W, and the Cu of sputter one deck 400nm
0.48In
0.52Alloy firm is in Cu
0.73Ga
0.27The alloy firm surface, the Cu that follows at sputter one deck 100nm
0.73Ga
0.27The Cu of alloy firm and 400nm
0.48In
0.52Alloy firm, the last Cu of sputter one deck 150nm again
0.73Ga
0.27Alloy firm, these five layers alloy firm that piles up alternately constitute Cu
0.48In
0.52/ Cu
0.73Ga
0.27Stacked structures is for making the predecessor of copper-indium-gallium-selenium compound layer.Five layers that complete are piled up Cu alternately
0.48In
0.52/ Cu
0.73Ga
0.27Structure can obtain the Cu of uniform film thickness
0.48In
0.52/ Cu
0.73Ga
0.27Predecessor piles up rete, and its thickness is about about 1150nm.Subsequently with these five layers of Cu that piles up alternately
0.48In
0.52/ Cu
0.73Ga
0.27Pile up rete and take out, and move into immediately in the selenizing stove, then feed the argon gas of 150cc/min, this inert gas shielding is piled up Cu for five layers alternately
0.48In
0.52/ Cu
0.73Ga
0.27It is not oxidized that predecessor piles up rete, and with 40 ℃/min programming rate to Cu
0.48In
0.52/ Cu
0.73Ga
0.27Predecessor piles up the rete heating, when temperature arrives 350 ℃, holds warm 60min, changes into copper gallium indium alloy-layer so as to predecessor being piled up rete.Then again with the programming rate heating copper gallium indium alloy-layer to 550 of 15 ℃/min ℃, and hold warm 60min, when carrying out above-mentioned intensification, be same as and produce selenium steam in the selenizing stove and keep selenium steam more than supersaturated vapor is pressed, and then implement the selenizing program and with copper gallium indium alloy-layer and selenium element reaction and transform into copper gallium indium selenium compound layer at copper gallium indium alloy-layer.This copper gallium indium selenium compound layer can be finished the making of copper gallium indium selenium compound layer in forming the back at the selenizing descent of temperature.
Embodiment 3:
The glass substrate that will contain one deck adhesion coating, with sputtering way with the molybdenum film sputter on adhesion coating, this molybdenum film thickness is 600nm, and adhesion coating can be as metal or its alloy firms such as first molybdenum film, Ti, Ta, Cr, Co, Ni and W in the embodiment 1.Then, again with DC sputtering way making Cu as shown in Figure 3
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27Predecessor piles up rete on molybdenum film, and this predecessor stacked film is to utilize Cu
0.73Ga
0.27With Cu
0.48In
0.52Alloy target material is a precursor material, earlier at the Cu with 160W power sputter one deck 100nm of piling up on the rete that comprises on molybdenum film and the glass substrate
0.73Ga
0.27Alloy firm reduces power subsequently to 60W, and the Cu of sputter one 600nh
0.48In
0.52Alloy firm is in Cu
0.73Ga
0.27The Cu of sputter one deck 200nm is again followed on the alloy firm surface
0.73Ga
0.27Alloy firm, these three layers alloy firm that piles up alternately constitute Cu
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27Predecessor piles up rete, wherein Cu
0.73Ga
0.27Alloy firm and Cu
0.48In
0.52Alloy firm thickness is respectively 300nm and 600nm.Subsequently, will comprise the Cu that this completes
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27Predecessor piles up the glass substrate of rete inserts in the vacuum selenizing stove, and with vacuum pump extract air earlier this moment, makes vacuum selenizing stove force value to 1x10
-6Torr is in extracting the process of air, to containing Cu
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27The glass substrate of predecessor stacked film heats, and firing rate is 20 ℃/min, as glass substrate and Cu
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27When the predecessor stacked film was heated to 300 ℃, alloy firm produced mutual diffusion and impels ternary alloy three-partalloy to produce, and this moment is by three layers of Cu
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27The predecessor stacked film will transform into a bronze medal gallium indium alloy-layer, when reaching 30min for 300 ℃, can make Cu as holding temperature
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27The predecessor stacked film fills a part mixing.At this moment, again copper gallium indium alloy-layer is heated to 520 ℃, firing rate is 25 ℃/min, when heating, the argon gas that feeds 5sccm is for carrying gas, and utilize argon gas to take selenium steam out of the selenium element thermal treatment zone, so that selenium steam is imported in the selenizing cavity, and must be earlier by a plasma district before entering the selenizing cavity, utilize the characteristic of the high knot of plasma from rate, selenium steam is carried out cracking to produce ionic state selenium, this ionic state selenium can arrive copper gallium indium alloy-layer surface by diffusion fast, enter alloy-layer inside by the alloy-layer diffusion into the surface again, this ionic state selenium and copper gallium indium alloy-layer react on and generate copper gallium indium selenium compound layer on the molybdenum electrode, can obtain complete copper gallium indium selenium compound layer after 520 ℃ are held warm 60 minutes.Resulting copper gallium indium selenium compound layer has high crystalline equally in this enforcement, and is chalcopyrite (chalcopyrite) structure.Utilize the vacuum selenizing to handle the copper gallium indium selenium compound layer of processing procedure made, when the selenizing temperature can produce copper gallium indium selenium compound structure in time more than 480 ℃.Should be higher than 520 ℃ with present embodiment selenizing temperature, hold on the temperature time and should finish to guarantee selenizing greater than 30min in selenizing, the preferable selenizing time is 60min.In alloying process, make Cu in addition
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27Stacked structures fills part a temperature of mixing should be higher than 200 ℃, should be with the preferable as can be known alloying temperature of the result of present embodiment at 300 ℃, and it is held the temperature time and should be higher than 10min.In the present embodiment, with reference to the observation of scanning type electron microscope, whole thickness is about the Cu of 800 nanometers
0.73Ga
0.27/ Cu
0.48In
0.52/ Cu
0.73Ga
0.27The surface roughness Ra of predecessor stacked film is about 150nm.
Comparative example 1:
Will be once the glass substrate of cleaning, with sputtering way with the molybdenum film sputter on glass substrate, this molybdenum film thickness is 1000nm.Then, the CuGa/In/CuGa predecessor of making as shown in Figure 1 with the DC sputtering way piles up rete on molybdenum film again, this predecessor stacked film is to utilize Cu and Ga alloy target material to be precursor material, earlier at the Cu with 160W power sputter one deck 100nm of piling up on the rete that comprises on molybdenum film and the glass substrate
0.78Ga
0.22Alloy firm reduces power subsequently to 60W, and the In metal level of sputter one 500nm is in Cu
0.78Ga
0.22The Cu of sputter one deck 300nm is again followed on the alloy firm surface
0.78Ga
0.22The alloy firm alloy firm, these three layers alloy firm that piles up alternately constitute Cu
0.78Ga
0.22/ In/Cu
0.78Ga
0.22Predecessor piles up rete, wherein Cu
0.78Ga
0.22Alloy firm and In thickness of metal film are respectively 400nm and 500nm.Subsequently, will comprise the Cu that this completes
0.78Ga
0.22/ In/Cu
0.78Ga
0.22Predecessor piles up the glass substrate of rete inserts in the vacuum selenizing stove, and with vacuum pump extract air earlier this moment, makes vacuum selenizing stove force value to 1x10
-6Torr is in extracting the process of air, to containing Cu
0.78Ga
0.22/ In/Cu
0.78Ga
0.22The glass substrate of predecessor stacked film heats, and firing rate is 20 ℃/min, as glass substrate and Cu
0.78Ga
0.22/ In/Cu
0.78Ga
0.22When the predecessor stacked film was heated to 300 ℃, alloy firm produced mutual diffusion and impels ternary alloy three-partalloy to produce, and this moment is by three layers of Cu
0.78Ga
0.22/ In/Cu
0.78Ga
0.22The predecessor stacked film will transform into a bronze medal gallium indium alloy-layer, when reaching 30min for 300 ℃, can make Cu as holding temperature
0.78Ga
0.22/ In/Cu
0.78Ga
0.22The predecessor stacked film fills a part mixing.Then again with the programming rate heating copper gallium indium alloy-layer to 550 of 15 ℃/min ℃, and hold warm 60min, when carrying out above-mentioned intensification, in the selenizing stove, produce simultaneously selenium steam and keep selenium steam press in supersaturated vapor above avoiding the gaseous state selenides to produce, and then at copper gallium indium alloy-layer execution selenizing program and selenium element reaction and transform into copper gallium indium selenium compound layer.This copper gallium indium selenium compound layer can be finished the making of copper gallium indium selenium compound layer in forming the back at the selenizing descent of temperature.In this comparative example, be about the Cu of 900 nanometers with reference to the whole thickness of the observation of scanning type electron microscope
0.78Ga
0.22/ In/Cu
0.78Ga
0.22The surface roughness Ra of predecessor stacked film is about 700nm.
Performance with reference to the surface roughness of different predecessor stacked films among comparative example 1 and the embodiment 3, the manufacture method that is appreciated that the copper gallium indium selenium compound film that this case invention is provided can only be produced the predecessor stacked film that surface roughness is not higher than 200Ra, thereby can improve the surface roughness of resulting copper gallium indium selenium compound film, and improve its battery efficiency and photoelectric conversion efficiency when thin-film solar cell applications.
Though the present invention discloses as above with preferred embodiment; so it is not in order to limit scope of the present invention; any personnel that are familiar with this technology; without departing from the spirit and scope of the present invention; when can doing a little change and retouching, so protection scope of the present invention is as the criterion when looking the scope that claims define.
Claims (22)
1. the manufacture method of a copper-indium-gallium-selenium compound membrane is characterized in that, comprising:
One substrate is provided;
Form an adhesion coating on this substrate;
Form a metal electrode layer on this adhesion coating;
Form a predecessor and pile up rete on this metal electrode layer, wherein this predecessor piles up rete and comprises a plurality of copper gallium alloy layers and be folded at least one copper and indium alloy layer between those copper gallium alloy layers;
Implement a tempering program, to pile up rete be a bronze medal indium gallium alloy layer to transform this predecessor; And
Implementing a selenizing program, is a copper-indium-gallium-selenium compound layer to transform this copper indium gallium alloy layer.
2. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, forms this adhesion coating and comprises a molybdenum layer.
3. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 2 is characterized in that, forms this adhesion coating and is included in formation one molybdenum layer under the pressure of 6～12mtorr.
4. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, forms this adhesion coating and comprises a metal level that forms titaniferous, tantalum, cobalt, chromium, nickel, tungsten or its alloy.
5. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this adhesion coating has the thickness between the 50-600 nanometer.
6. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this adhesion coating and this metal electrode layer have and be not more than one of 1200 nanometers and combine thickness.
7. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, those copper gallium alloy layers that this predecessor piles up in the rete have a chemical formula Cu
yGa
1-y, and 0.22＜y＜0.9.
8. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this at least one copper and indium alloy layer that this predecessor piles up rete has a chemical formula Cu
xIn
1-x, and 0.04＜x＜0.5.
9. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, the copper in this copper indium gallium alloy layer has the element ratio between 0.6～1.3.
10. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, the gallium element in this copper indium gallium alloy layer is between 0.1～0.5 element ratio.
11. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this selenizing program is to implement being higher than under 450 ℃ the temperature.
12. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this selenizing program was implemented about 10～100 minutes.
13. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1, it is characterized in that it is the method for employing sputter, evaporation, plating or its combination and being formed on this metal electrode layer that this predecessor piles up those copper gallium alloy layers and this at least one copper and indium alloy layer in the rete.
14. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this copper-indium-gallium-selenium compound layer has a surface roughness that is not higher than 200Ra.
15. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this selenizing program is to adopt ionic state selenium and copper indium gallium alloy layer to carry out selenylation reaction, to form this copper-indium-gallium-selenium compound layer.
16. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 15 is characterized in that, the plasma selenium of this ionic state selenium for dissociating through plasma.
17. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this selenizing program is to carry out under 450 ℃-600 ℃ temperature.
18. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this selenizing program is between 1*10
-6Carry out under the pressure of torr to 10mtorr.
19. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this tempering program is to carry out under a temperature of 150 ℃-400 ℃.
20. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this tempering program was implemented about 10～80 minutes.
21. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this substrate is the substrate through wet-cleaned.
22. the manufacture method of copper-indium-gallium-selenium compound membrane according to claim 1 is characterized in that, this metal electrode layer comprises molybdenum.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103681960A (en) * | 2013-11-21 | 2014-03-26 | 山东希格斯新能源有限责任公司 | Multi-step sputtering process for preparation of CIG precursor layer of CIGS (copper indium gallium selenide) film |
| CN103828063A (en) * | 2011-08-10 | 2014-05-28 | 阿森特太阳能技术公司 | Multilayer thin-film back contact system for flexible photovoltaic devices on polymer substrates |
| CN103872156A (en) * | 2012-12-17 | 2014-06-18 | 财团法人工业技术研究院 | Multi-layer stacked light absorption film, manufacturing method thereof and solar cell |
| US9780242B2 (en) | 2011-08-10 | 2017-10-03 | Ascent Solar Technologies, Inc. | Multilayer thin-film back contact system for flexible photovoltaic devices on polymer substrates |
-
2009
- 2009-06-17 CN CN2009101491404A patent/CN101924162A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103828063A (en) * | 2011-08-10 | 2014-05-28 | 阿森特太阳能技术公司 | Multilayer thin-film back contact system for flexible photovoltaic devices on polymer substrates |
| US9780242B2 (en) | 2011-08-10 | 2017-10-03 | Ascent Solar Technologies, Inc. | Multilayer thin-film back contact system for flexible photovoltaic devices on polymer substrates |
| CN103872156A (en) * | 2012-12-17 | 2014-06-18 | 财团法人工业技术研究院 | Multi-layer stacked light absorption film, manufacturing method thereof and solar cell |
| CN103872156B (en) * | 2012-12-17 | 2016-04-27 | 财团法人工业技术研究院 | Multi-layer stacked light absorption film, manufacturing method thereof and solar cell |
| CN103681960A (en) * | 2013-11-21 | 2014-03-26 | 山东希格斯新能源有限责任公司 | Multi-step sputtering process for preparation of CIG precursor layer of CIGS (copper indium gallium selenide) film |
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