CN101135040A - Method for preparing p-type copper-sulfur-containing transparent conductor film - Google Patents
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- CN101135040A CN101135040A CNA2007100388093A CN200710038809A CN101135040A CN 101135040 A CN101135040 A CN 101135040A CN A2007100388093 A CNA2007100388093 A CN A2007100388093A CN 200710038809 A CN200710038809 A CN 200710038809A CN 101135040 A CN101135040 A CN 101135040A
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Abstract
The present invention is pulse laser deposition (PLD) process for preparing p-type compound CuAlS2 in chalcopyrite structure and transparent doped conducting film. The PLD process prepares p-type compound CuAlS2 or doped film on the substrate of quartz glass, common glass or Si chip by using the compound block obtained through solid phase reaction and SPS sintering or no-pressure sintering as the target and under proper conditions of atmospheric pressure, substrate temperature, and laser strength and frequency. The prepared CuAlS2 film has p-type conductivity, high conductivity, high visible light transparency and other excellent optoelectronic performance, and may find its broad application foreground in electronics and optoelectronics.
Description
Technical field
The present invention relates to a kind of yellow copper structure Compound C uAlS of the p of can be used for type transparent conductor
2The preparation method of film.Belong to transparent conductive material (TCM) thin film technique field.
Background technology
Transparent conductor is a kind of material that has high optical transmittance and satisfactory electrical conductivity in the visible region.1907, Badeker reported translucent conduction CdO material [K.Badeker, Ann.Phys.Leipzig1907,22,749] first, has caused people's attention.Up to during the Second World War, because military requirement, transparent conductive body is just paid attention to widely and is used.Transparent conductor all is oxide compound basically, also claim transparent conductive oxide (transparent conducting oxides, TCO).TCO can be divided into n type and p type two classes according to conductive characteristic.N type TCO material is as In
2O
3: Sn (ITO), SnO
2: F (FTO) and Zn:Al (AZO) have been widely used in plane demonstration, building and solar photovoltaic energy system [D.S.Ginley, C.Bright, eds., MRS Bulletin2000,25,15] as transparency electrode.Estimation according to statistics, nearly 25,000,000,000 dollars of the marketing that plane in 2004 shows, the importance of transparent conductor [the N.R.Lyman.Transparent Electronic Conductors that sees some from this; Electrochemical Society:Princeton, NJ, 1990,90-92,201].
Though n type TCO Development of Materials is comparative maturity and existing application widely, but the developing history of p type transparent conductor is ofer short duration, 1997, Kawazoe etc. reported p type TCO material---the CuAlO of first delafossite (delafossite) type structure on Nature
2[H.Kawazoe, M.Yasukawa, H.Hyodo, M.Kurita, H.Yanagi, and H.Hosono, Nature, 1997,389,939] have caused the research boom of p type TCO material, but there is no substantial development all the time, say nothing of important breakthrough.Research mainly concentrates on some oxide compounds (as Indium sesquioxide, zinc oxide and stannic oxide) and mixes, and accumulates in from CuAlO
2To NiO to SrCu
2O
2On system, and make slow progress.Up to 2000, with CuAlO
2The CuMO of same structure
2(M=Ga, Y, Sc, In) similar conduction property just is found [(1) N.Duan, A.W.Sleight, M.K.Jayaraj, J.Tate, Appl.Phys.Lett.2000,77,1325; (2) H.Yanagi, S.Inoue, K.Ueda, N.Hamada, H.Kawazoe, H.Hosono, J.Appl.Phys.2000,88,4159].Since the singularity of the electrical conduction mechanism and the structure of matter, the electric conductivity of these materials all lower (10
-2～10
-1S/cm) and improve relatively difficulty.Therefore, the exploration of p section bar material is progressively expanded to the other materials system, has p type electroconductibility [K.Ueda, S.Inoue as discovery LaCuOS such as Ueda in 2000, S.Hirose, H.Kawazoe, and H.Hosono, Appl.Phys.Lett.2000,77,2701], the adulterated La of Sr
1-xSr
xThe electric conductivity of CuOS is 1～2 * 10
-1S/cm[M.Yasukawa, K.Ueda, and H.Hosono, J.Appl.Phys.2004,95,3594], Yanagi etc. find that in 2003 (Q=S, electric conductivity Se) is 8.8 * 10 to BaCuFQ
-2S/cm and be p section bar material [H.Yanagi, andJ.Tate, Appl.Phys.Lett.2003,82,2814].Yet the conductivity of these materials is all not ideal enough (as p type CuAlO
2Be 1～2 * 10
-1S/cm, SrCu
2O
2Film is 5 * 10
-2S/cm[(1) N.R.Lyman.Transparent Electronic Conductors; Electrochemical Society:Princeton, NJ, 1997,90-92,201; (2) G.Thomas, Nature1997,389907], well below the n section bar material (ITO10 of commercialization
3～10
4S/cm) N, P or As doped p type ZnO film also become the research focus in recent years.Though people also adopt pulsed laser deposition (pulsed laser deposition, PLD), molecular beam epitaxy, metal organic chemical vapor deposition, prepared in various methods such as film growth such as magnetron sputtering go out high-quality ZnO film, but are difficult to obtain stable p-type ZnO film [(1) .Aoki, Y.Hatanaka, and D.C.Look.Appl.Phys.Lett.2000,76,3257. (2) X.L Guo, H.Tabata, and T.Kawai.Optical Materials, 2002,18,229. (3) T.M.Barnes, K.Olson, and C.A.Wolden.Appl.Phys.Lett.2005,86,112112. (4) Z.G.Ji, C.X.Yang, K.Liu, and Z.Z.Ye.J.Cryst.Growth, 2003,253,239. (5) J.G.Lu, Z.Z.Ye, F.Zhuge, Y.J.Zeng, B.H.Zhao, L.P.Zhu.Appl.Phys.Lett.2004,85,3134.].P type ZnO is in nonequilibrium state, the E of the adulterated ZnO of p type
F (p)(p-type pinning energy) far above the valence band top (valence band maxium, VBM), the fermi level E that in p type doping process, moves down
fAt first run into E
F (p), can produce " hole killer " (gap zinc and oxygen room) at material internal.Yanagi in 2003 etc. have reported and have contained chalcogenide ACu
2S
2(A=Ba is a p N-type semiconductorN material Sr), points out the adulterated BaCu of K
2S
2The normal temperature electric conductivity can reach 17S/cm[H.Yanagi, J.Tate, S.Park, C-H.Park, D.A.Keszler, Appl.Phys.Lett.2003,82,2814.].Though band of gas crack has only 2.3eV, but pointed out p type transparent conductor material (transparent conducting material, TCM) search research should not be confined to oxide compound again, sulfocompound also will become fabulous candidate's system [(1) F.Q.Huang, Ibers, J.Solid State Chem.2001,158,299. (2) F.Q.Huang, J.A.Ibers, Inorg.Chem., 2001,40,2602. (3) F.Q.Huang, P.Brazis, C.R.Kannewurf, J.A.Ibers, J.Amer.Chem.Soc., 2000,122,80.].
Say that from application point photovoltaic/photovoltaic industry (as solar photovoltaic energy system) development is advanced by leaps and bounds, but also has shortcomings such as energy conversion efficiency is low.In the solar photovoltaic energy system,, make to greatest extent in the solar energy access to plant, just be expected to increase significantly the efficient of photovoltaic device if enough n types of energy and p type TCO material superposition get up to make transparent cathode and anode respectively.In view of the above, the J.Wager of the U.S. etc. covers ito thin film [B.J.Norris on the zno-based plate, J.Anderson, J.F.Wager, et al.Journal of Physics D2003,36, L105], the human n type ZnO such as H.Kawazoe of Japan prepare successfully transparent diode [H.Kawazoe, H.Yanagi with p type SCO formation heterojunction, K.Ueda, andH.Hosono, MRS Bulletin2000,25,28], thereby caused people's attention in abstracto, but these transparent diodes have no application value, its basic reason is not find desirable p section bar material.In addition, p type conductor material can also and be made photorectifier as the generating multifunctional window, and in the energy more and more severeer future, this will be a great scientific-technical progress.
Pulsed laser deposition (PLD) is a kind of physical film deposition method of general comparative maturity, it is a kind of film process based on the ablation plated film, promptly very high laser energy moment is transferred to the very little position of target material surface, cause its temperature to be higher than the distillation limit, target comes out and utilizes remaining kinetic energy to move to pole plate (being substrate) surface and the formation of deposits film with regard to ablated like this.PLD has very high validity and universality, but generally only is used for the deposition oxide film, and the study on deposition of sulfide film is not appeared in the newspapers.
Based on more than, the exploratory development of p type copper-sulfur-containing transparent conductor material is of great immediate significance, research is prepared high-quality cupric sulphur p type transparent conductor film with the PLD technology and is also had important science background and vast potential for future development, thereby is guided out purpose of the present invention.
Summary of the invention
The object of the invention is to provide a kind of preparation method of yellow copper structure material film of the p of can be used for type transparent conductor.The design of invention is: utilize the high energy laser beam in pulsed laser deposition (PLD) the physical film deposition method, bombardment is by plasma (SPS) sintering of solid state reaction and discharge or the copper sulphur compound target that is obtained by solid state reaction and pressureless sintering, high energy laser beam is transferred to the very little zone of target material surface in moment with energy, cause its temperature to be higher than the distillation limit, make target evenly ablate, and utilize remaining kinetic energy to move to substrate surface and the compound film of formation of deposits cupric sulphur.
The present invention selects CuAlS
2And doped compound (being doped to example with Zn with the Cu doping) adopts PLD to prepare Cu as target
1+xAl
1-xS
2(0＜x≤0.15) and CuAl
1-xZn
xS
2(0＜x≤0.10) p type transparent conductive film provides a kind of photoelectric properties superior p type transparent conductor.PLD is a kind of method for manufacturing thin film of the principle based on pulse laser beam.With CuAlS
2Be example, it is as follows to utilize PLD to prepare the concrete steps of cupric sulphur compound p type transparent conductive film:
1, target preparation:
Select for use high-purity simple substance powder or corresponding sulfide by CuAlS
2Chemical constitution or Cu auto-doping or the adulterated cupric sulphur compound of Zn prepare burden (the Al powder as 99.99%, 99.7% Cu powder, 99.999% S powder and 99.999% Zn powder or 99% Cu
2S and 99% Al
2S
3Press CuAlS
2And Cu mixes and the adulterated chemical constitution proportioning of Zn is prepared burden), the compound quartz glass tube of packing into is through vacuumizing (less than 10
-2Pa) back encapsulation, 650 ℃～850 ℃ are carried out solid state reaction, and the reaction times is 24～96h.Powder grinds encapsulation again behind the open pipe, carries out the solid state reaction second time, condition and preceding similar, with resulting pure phase powder, pressure with 40～60MPa under 700～850 ℃ carries out the SPS sintering, or the quartz glass tube of packing into behind the 200Mpa isostatic pressing, through vacuumizing (less than 10
-2Pa) encapsulation in 700～900 ℃ of following sintering 6-24h, is finally made block; It is Cu that the adulterated cupric sulphur compound of described Cu auto-doping or Zn is formed general formula
1+xAl
1-xS
2Or CuAl
1-xZn
xS
2, 0.05≤x in the formula≤0.15.
2, film preparation:
The block that makes with step 1 is a target, is substrate with simple glass or silica glass or Si sheet, keeps high vacuum (10
-4Pa) or rare gas element such as nitrogen be working gas, air pressure keeps 10
-3Pa～10Pa, underlayer temperature are controlled between the room temperature to 600 ℃, and laser energy is 120mJ, and frequency control is at 1Hz～5Hz, and depositing time is 20min～80min, and target and substrate distance are about 6cm.Can wait thickness and the quality of controlling film by the distance of understanding depositing time, laser energy and frequency, operating air pressure and target and substrate according to actual needs.The thickness of prepared film is 10nm～200nm.
The performance characterization of film and evaluation
1, the thing of film characterizes with pattern
Gained film sample of the present invention is become and pattern by the scanning electron microscopic observation film thickness.Used Electronic Speculum model is JSM-6700F; By X-ray powder diffraction instrument (Rigaku D/Max-2550V) analysed film thing phase.
2, optical property characterizes
With the transmitance of the resulting film of the present invention with ultraviolet-visible-near infrared spectrometer (HITACHIUV-3010PC) testing film.
3, electric property characterizes
After gained film sample point silver electrode of the present invention, carry out the conductivity evaluation with classical testing method such as four-point methods.And determine the conduction type of sample by the test of Seebeck coefficient.
Table 1 CuAlS provided by the invention
2And the room temperature electric property of doping film and gathering of film
Description of drawings
Fig. 1 CuAlS
2The XRD figure of film.
Fig. 2 CuAlS
2And the doping film sample see through spectrum.
Fig. 3 Ar gas atmosphere is 10Pa, and underlayer temperature is 400 ℃ of CuAlS of preparation down
2And the specific conductivity of doping film sample and temperature relation curve.
Fig. 4 SEM microstructure photograph.
Fig. 5 hydrogen capacity and pressure dependence curve.
Embodiment
Introduce embodiments of the invention below, but the present invention only limits to embodiment absolutely not.
Embodiment 1:
The CuAlS that adopts vacuum solid state reaction and SPS sintering to obtain
2Circular block is a target, and the target diameter is 15mm.Quartz glass plate is substrate (substrate), and successively through deionized water, rare HCL, acetone, dehydrated alcohol, deionized water ultrasonic cleaning respectively 20 minutes.Fixedly target material surface and substrate surface distance is about 5cm.
Keep high vacuum (10
-4Pa), underlayer temperature is controlled at 600 ℃, and laser energy is 120mJ, and initial frequency is 1Hz, pre-deposition 5min, and changing frequency again is 5Hz, and depositing time is 60min, and deposition finishes, and treats that temperature reduces to room temperature, takes out, and promptly gets amorphous CuAlS
2Film (XRD sees Fig. 1).Film thickness is not very even, thin edge, and thick middle, scanning electron microscopic observation is between 50～200nm.(200nm～3000nm) sees Fig. 2, and transmitance is more than 70% in the visible-range, and conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of), and room-temperature conductivity is about 1s/cm (seeing Table 1) to see through spectrum.
Embodiment 2:
Similar to embodiment 1, it is work atmosphere that difference is to adopt Ar, and operating air pressure is 10Pa, the amorphous CuAlS that obtains
2(XRD is similar to embodiment 1) film thickness is even, and thickness is 100nm, and ultraviolet-near infrared spectrum (Fig. 2) that sees through shows that average transmittances is greater than 75% in the visible-range.Conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of), and (150K～350K) specific conductivity is seen Fig. 3 to alternating temperature, and room-temperature conductivity (sees Table 1) about 2S/cm.
Embodiment 3:
Similar to embodiment 2, it is substrate that difference only is to adopt the Si sheet, obtains amorphous CuAlS
2Film (XRD is similar to embodiment 1), film thickness record room-temperature conductivity and embodiment 2 close (seeing Table 1) about 100nm, conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of).
Embodiment 4:
Similar to embodiment 2, difference only is that substrate temperature is controlled at 400 ℃, the CuAlS that obtains
2Film is non-crystalline state (XRD is similar to embodiment 1), film thickness is about 80nm, visible light transmissivity is slightly larger than embodiment 2 (see figure 2)s, and conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of), and room-temperature conductivity is a little more than embodiment 2 (seeing Table 1).Specific conductivity varies with temperature curve and sees Fig. 3.
Embodiment 5:
Similar to embodiment 4, it is substrate that difference only is to adopt simple glass, and the result who obtains is identical with embodiment 4.
Embodiment 6:
Similar to embodiment 2, difference only is that substrate temperature is controlled at 200 ℃, the noncrystal membrane that obtains (XRD is similar to embodiment 1) thickness is about 40nm, visible light transmissivity is greater than 85%, conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of), and specific conductivity is significantly smaller than embodiment 2 (seeing Table 1).
Embodiment 7:
Similar to embodiment 2, difference only is that underlayer temperature is room temperature (about 20 ℃), the amorphous CuAlS that obtains
2Thickness is about 10nm for film (XRD is similar to embodiment 1), and visible light transmissivity is higher than 90%, and conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of), and specific conductivity can not tested on testing tool.
Embodiment 8:
Similar to embodiment 4, difference is to adopt Cu
1.08Al
0.92S
2(8%Cu auto-doping sample) circular block is a target.Obtain the adulterated CuAlS of Cu
2Noncrystal membrane (XRD is similar to embodiment 1), thickness and visible light transmissivity are close with embodiment 4, conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of), and room-temperature conductivity is higher than embodiment 4 (seeing Table 1), and specific conductivity varies with temperature curve and sees Fig. 3.
Embodiment 9:
Similar to embodiment 4, difference is to adopt Cu
1.15Al
0.85S
2(15%Cu auto-doping sample) circular block is a target.Obtain the adulterated CuAlS of Cu
2Noncrystal membrane (XRD is similar to embodiment 1), thickness and visible light transmissivity are close with embodiment 4, and conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of), and room-temperature conductivity (sees Table 1) between embodiment 4 and embodiment 8.Specific conductivity varies with temperature curve and sees Fig. 3.
Embodiment 10:
Similar to embodiment 4, difference is to adopt CuAl
0.90Zn
0.10S
2(10%Zn doped samples) circular block is a target, obtains the adulterated CuAlS of Zn
2Noncrystal membrane (XRD is similar to embodiment 1), thickness and visible light transmissivity are close with embodiment 4, and conducting performance test shows that it has p type electroconductibility (in the table 1 Seebeck coefficient on the occasion of), and room-temperature conductivity is between embodiment 4 and embodiment 8.Specific conductivity varies with temperature curve and sees Fig. 3.
Table 1CuAlS
2And the preparation condition and the room temperature electric property of doping film sample
| Thin film composition | Underlayer temperature (℃) | Prepared atmosphere | Pressure (Pa) | The Seebeck coefficient room-temperature conductivity | Film thickness (nm) | |
| (μVK -1) | (S/cm) | |||||
| CuAlS
2(embodiment 1) CuAlS
2(embodiment 2) CuAlS
2(embodiment 3) CuAlS
2( |
600 600 600 400 200 room temperatures 400 400 400 | - Ar Ar Ar Ar Ar Ar Ar Ar | 10 -410 10 10 10 10 10 10 10 | +37 +38 +36 +35 +39 +41 +34 +38 +39 | 0.96 1.85 1.91 2.64 0.02 5.03 2.69 3.12 | 50- |
Claims (9)
1. the preparation method of a p type cupric sulphur transparent conductive film, it is characterized in that utilizing the high energy laser beam in the pulsed laser deposition film, bombardment is by solid state reaction and SPS sintering or the copper sulphur compound target that obtained by solid state reaction and pressureless sintering, moment high energy laser beam with energy transfer to the surface the zonule, make target evenly ablate, and utilize remaining kinetic energy to move to substrate surface and the compound film of formation of deposits p type cupric sulphur.
2. by the preparation method of the described p type of claim 1 cupric sulphur transparent conductive film, it is characterized in that processing step is:
(a) simple substance Cu, Al and S powder or Cu
2S and Al
2S
3Sulfide is pressed CuAlS
2The chemical constitution batch mixing and the quartz glass tube of packing into, encapsulation after vacuumizing, in 650 ℃ of-850 ℃ of solid state reactions, powder grinds encapsulation again behind the open pipe, carries out the solid state reaction second time in 650 ℃-850 ℃ again, resulting pure phase powder, carry out the SPS sintering at 750 ℃-850 ℃ with 40-60MPa pressure, or the quartz glass tube of behind the 200MPa isostatic pressing, packing into, through vacuumizing encapsulation, in 700 ℃ of-900 ℃ of pressureless sinterings, make CuAlS
2Block;
(b) block made from step (a) is a target, is substrate with simple glass or silicon chip, 10
-4Pa vacuum or air pressure are 10
-3In the rare gas element of pa～10Pa, carry out pulsed laser deposition, laser energy is 120mj, and frequency is 1HZ-5HZ, and underlayer temperature is controlled at room temperature to 600 ℃, and depositing time is 20min～80min, finally makes p type copper-sulfur-containing transparent conductor film.
3. by the preparation method of the described p type of claim 2 cupric sulphur transparent conductive film, the purity that it is characterized in that described simple substance powder is respectively that the Al powder is 99.99%, and Cu powder 99.7%, S powder are 99.999%; Described Cu
2S and Al
2S
3The purity of sulfide＞99%.
4. by the preparation method of the described p type of claim 2 cupric sulphur transparent conductive film, the time that it is characterized in that solid state reaction is 24-96h.
5. by the preparation method of the described p type of claim 2 cupric sulphur transparent conductive film, it is characterized in that distance is 4-6cm between described target and the substrate; Prepared film thickness is 10-200nm, and is non-crystalline state.
6. by the preparation method of the described p type of claim 1 cupric sulphur transparent conductive film, it is characterized in that processing step is:
(a) simple substance Cu, Al or Zn, S powder or Cu
2S and Al
2S
3Sulfide and corresponding powder become batch mixing and the quartz glass tube of packing into by Cu auto-doping or the adulterated cupric sulphur compound of Zn, encapsulation after vacuumizing, in 650 ℃ of-850 ℃ of solid state reactions, powder grinds encapsulation again behind the open pipe, carry out the solid state reaction second time in 650 ℃-850 ℃ again, resulting pure phase powder, carry out the SPS sintering at 750 ℃-850 ℃ with 40-60MPa pressure, or the quartz glass tube of behind the 200MPa isostatic pressing, packing into, through vacuumizing encapsulation, in 700 ℃ of-900 ℃ of pressureless sinterings, make copper sulphur-cake body; The composition general formula of described Cu auto-doping or the adulterated cupric sulphur compound of Zn is Cu
1+xAl
1-xS
2Or CuAl
1-xZn
xS
2, 0.05≤x in the formula≤0.15;
(b) block made from step (a) is a target, is substrate with simple glass or silicon chip, 10
-4Pa vacuum or air pressure are 10
-3In the rare gas element of pa～10Pa, carry out pulsed laser deposition, laser energy is 120mj, and frequency is 1HZ-5HZ, and underlayer temperature is controlled at room temperature to 600 ℃, and depositing time is 20min～80min, finally makes p type copper-sulfur-containing transparent conductor film.
7. by the preparation method of the described p type of claim 6 cupric sulphur transparent conductive film, the purity that it is characterized in that described simple substance powder is respectively that the Al powder is 99.99%, and Cu powder 99.7%, S powder are 99.999%; The Zn powder is＞99.999%; Described Cu
2S and Al
2S
3The purity of sulfide＞99%.
8. by the preparation method of the described p type of claim 6 cupric sulphur transparent conductive film, the time that it is characterized in that solid state reaction is 24-96h.
9. by the preparation method of the described p type of claim 6 cupric sulphur transparent conductive film, it is characterized in that distance is 4-6cm between described target and the substrate; Prepared film thickness is 10-200nm, and is non-crystalline state.
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| CN100588737C (en) | 2010-02-10 |
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