CN100499176C - Multiple layer modulation-doped ZnO-MgZnO transparent conductive oxide thin film - Google Patents
Multiple layer modulation-doped ZnO-MgZnO transparent conductive oxide thin film Download PDFInfo
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- CN100499176C CN100499176C CNB2006100226643A CN200610022664A CN100499176C CN 100499176 C CN100499176 C CN 100499176C CN B2006100226643 A CNB2006100226643 A CN B2006100226643A CN 200610022664 A CN200610022664 A CN 200610022664A CN 100499176 C CN100499176 C CN 100499176C
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Abstract
The invention relates to a transparent conductive oxide film with a multilayer modulation doping and pertains to structure design of a semiconductor apparatus. At the back of the B1 in a ZnO buffer layer, a modulation-doped layer with a repeated periodicity is added (comprising an MgxZn<1-x>O: Al doping layer D, an MgxZn<1-x>O barrier layer B and a ZnO: Oy modulation layer M). The thickness of the buffer is 10-20nm and the thickness of the doping layer D and the modulation layer M are both 2-6nm and the thickness of the barrier layer is 1-3nm; the coping concentration of the Al is less than 5% and the content of the Mg is 10-33%. The multilayer modulation doping structure dose not leads to the loss of the optical transmissivity of the semiconductor apparatus, can solve the problem of the impurity iron scattering in the transparent conductive film, increases the mobility of the carrier hall and greatly improves the electricity performance of the apparatus. The invention not only helps the photoelectric converting device (such as a solar cell) to develop towards the direction of large area and high efficiency, but also helps the transparent electrical apparatus (such as a liquid crystal display) to develop towards the direction of high performance.
Description
Technical field
The invention belongs to a kind of structural design of transparent conductive oxide film, particularly a kind of layer modulation-doped zno-based transparent conductive oxide film.
Background technology
Transparent conductive oxide ZnO (TCOs) film has visible region transmitance height (〉 80%), the big (〉 3eV of energy gap) good photoelectric characteristic, the electrode of Chang Zuowei liquid crystal flat panel display, solar cell.
Along with developing rapidly of large tracts of land, high efficiency electrooptical device and high-performance transparent electronics, press for the character of improving transparent conductive material, particularly photoelectric characteristic, as conductivity and transmitance.Because the change and the control of optical transmittance can realize that therefore, what people more paid close attention to is the electrical properties of transparent conductive film, mainly is the size of resistivity (ρ) by the thickness that changes film.By formula ρ=(ne μ)
-1As seen, the size of resistivity depends mainly on carrier concentration n and mobility [mu] (=e τ/m
*).Increase carrier concentration n or mobility [mu] and can both improve conductivity of electrolyte materials, still, further increase carrier concentration n, can bring the adverse effect of two aspects, the scattering that can increase ionic impurity reduces mobility on the one hand; On the other hand, because the absorption of free carrier can cause transmitance to reduce.Thereby feasible way is by increasing relaxation time τ or reducing effective mass m
*Improve mobility [mu], in real work, show as the film of the excellent crystalline quality of preparation, as bigger crystal grain, less stress etc.Yet the transparent conductive film mobility that conventional doping means obtain is 10～60cm
2V
-1s
-1, this is starkly lower than the theoretical limit 90cm of the conductive oxide film of people such as Bellingham expection
2V
-1s
-1(see J Mater Sci Lett, 1992.11:263)
In the seventies in 20th century, in order to increase GaAs-Al
xGa
1-xThe mobility of As superlattice, people such as Dingle proposed " modulation doping " notion (see Appl Phys Lett, 1978,33:665), subsequently, modulation doping is applied to some semiconducting compounds, as GaAs-Al
xGa
1-xAs, Si-Si
xGe
1-x, GaN-Al
xGa
1-xN, and obtained success.There is researcher to propose the notion of modulation doping is applied to the zno-based transparent conductive film, but fails to obtain satisfied result.As, Tominaga etc. have prepared ZnO:Al-ZnO:O
v(O
vBe the oxygen room) the multi-layer transparent conductive oxide film, be similar to modulation-doped structure, but its mobility is not high, approximately 30cm
2V
-1s
-1(see Thin Solid Films, 1998,334:35).Main cause is that the energy gap of doped layer and undoped layer is more approaching, spatially can not be effectively electronics and foreign ion separately, thereby reduce the influence of foreign ion scattering.
Summary of the invention
Therefore, the objective of the invention is in order to solve foreign ion scattering problem in the transparent conductive film, improve modulation doping zno-based transparent conductive film, propose a kind of structural design of layer modulation-doped ZnO-MgZnO transparent conductive oxide film.
For realizing the present invention, technical scheme of the present invention adopts Mg
xZn
1-xO:Al/Mg
xZn
1-xO/ZnO:O
vStructure is as modulate-doped layer, and adds the ZnO resilient coating between substrate and modulate-doped layer.Periodicity emphasis multiple modulation doped layer can get layer modulation-doped ZnO-MgZnO transparent conductive oxide film.
Adopt the Mg of broad energy gap
xZn
1-xO:Al (energy gap can up to～3.9eV) as doped layer, ZnO:Ov (the energy gap～3.3eV) as modulating layer of less energy gap does not mix, improved layer modulation-doped transparent conductive oxide structure, spatially effectively electronics and foreign ion are separated, greatly increase the charge carrier Hall mobility, improve conductivity of electrolyte materials, thereby greatly improve the electrical properties of device.
Description of drawings
Fig. 1 is a n type modulation doping semiconductor principle schematic diagram.
Symbolic representation among the figure is respectively: 1 is Mg
xZn
1-xO:Al, 2 is ZnO:O
v, 3 is foreign ion, and 4 is electron gas, and 5 is Fermi level, and 6 is conduction band, 7 is valence band.
Fig. 2 is the n type ZnO-Mg in two cycles
xZn
1-xO modulation doping transparent conductive oxide structural representation.
Symbolic representation among the figure is respectively: S is a substrate, and B1 is the ZnO resilient coating, and D is Mg
xZn
1-xO:Al doped layer, B are Mg
xZn
1-xThe O barrier layer, M is the ZnO:Ov modulating layer.
Embodiment
Below in conjunction with accompanying drawing principle of the present invention and structure formation are described in further detail.
Principle of the present invention as shown in Figure 1, Mg
xZn
1-xO:Al 1 is as the doped layer of broad energy gap, ZnO:O
v2 as not mixing the modulating layers of less energy gap, presss from both sides a Mg who does not mix Al therebetween
xZn
1-xO barrier layer (very thin not shown), so conduction band electron does not form two-dimensional electron gas 4 at the interface, but leniently energy gap thin layer 1 is transported to narrow energy gap layer 2, and be limited in the narrow potential well, realized on the space that foreign ion 3 separates with electronics, greatly reduce the scattering of foreign ion, thereby increased mobility greatly.
In Fig. 2, (1) deposition layer of ZnO resilient coating B1 on substrate S; (2) deposit Mg subsequently
xZn
1-xO:Al doped layer D, content 0.1≤x≤0.33 of Mg, the content of Al can not be too high, otherwise can cause the variation that can be with, its content＜5%; (3) deposit a unadulterated Mg again
xZn
1-xO is as barrier layer B; (4) deposit ZnO:O at last
vAs the less energy gap modulating layer M that do not mix, finished one-period like this, repeating step (2)～(4) just obtain the transparent conductive oxide of multilayer ZnO-MgZnO modulation doping.
The ZnO resilient coating B1 of deposition high-quality (～15nm), help Mg subsequently
xZn
1-xO:Al doped layer D presses hexagonal structure extension (or according to qualifications) growth.About choosing of Mg content in the broad energy gap doped layer, be because the ternary system compound Mg
xZn
1-xO exists MgO to separate out problem with six sides/cube phase transformation mutually.As x≤0.33, Mg
xZn
1-xO is a hexagonal structure, maximum energy gap～3.9eV; 0.45 x〉0.33, will there be MgO to separate out; X〉0.45, Mg
xZn
1-xO changes cubic structure into by hexagonal structure.Deposit not doped with Mg subsequently
xZn
1-xO can weaken the influence of adjacent foreign ion scattering far away to mobility as barrier layer B since the lattice mismatch of ZnO and MgO very little～0.1%, so Mg content is identical with doped layer D among the B of barrier layer.D thickness 2～6nm, B thickness 1～3nm is in order to prevent the mutual scattering of subband, M thickness≤6nm, the gross thickness 300～800nm of modulate-doped layer.
The effect of layer modulation-doped transparent conductive oxide film is to realize electronics transporting from the doped layer to the undoped layer among the present invention, spatially isolate foreign ion and electronics, reduce foreign ion and interelectric scattering, increase the mobility of charge carrier rate, improve its conductivity, fundamentally reach the purpose of improving the device electrical properties.In addition, by controlled doping concentration, can change the transmitance of infrared band, also be the ideal material of domestic energy-saving and national defence infrared stealth therefore.
The backing material S that adopts in the embodiment of the invention is sapphire or glass, through cleaning and pre-sputter, can prepare layer modulation-doped ZnO-MgZnO transparent conductive oxide film.
Embodiment one:
Use radio frequency sputtering method:
Adopt the cosputtering device, 3 sputtering sources be set on this device, distinguish splash-proofing sputtering metal Zn target (99.99%), metal A l target (99.99%) and (or) 99.999% Mg-Zn alloys target or Mg
xZn
1-xThe O ceramic target, wherein, the variable constituentsization of Mg in the Mg-Zn alloys target, Mg
xZn
1-xThe O ceramic target adopts ZnO powder (99.999%) and MgO powder (99.999%) to mix according to the component of Mg content 10%～33%, forms through grinding, forging and pressing, sintering.The material that sputters out from 1～2 target is pooled to substrate surface.Adopt different backing material S (glass, sapphire), substrate S needs to carry out pre-sputter clean before film forming, during sputter, makes the substrate S rotation and it is heated (room temperature to 700 ℃ adjustable), Ar and O
2Import via special breather pipe, again by controlling and regulate following condition and parameter:
The diameter phi 60mm of target
Distance～12cm between target and substrate
Base vacuum 2 * 10
-3Pa
Working gas Ar/O
2=1/0.2～1/1
80 ℃-600 ℃ of underlayer temperatures
Rate of film build 2～4nm/min
Sputtering power 20～300W
Can prepare layer modulation-doped ZnO-MgZnO transparent conductive oxide film.Concrete steps are: at first adopt reactive sputtering Zn target prepare high-quality ZnO resilient coating B1 (10～20nm), adopt again reaction cosputtering Zn-Mg alloys target (～50W) or cosputtering Mg
xZn
1-xO ceramic target (200W) and Al target (25～150W) preparation doped layer D Mg
xZn
1-xO:Al film 2～6nm, Al atomic concentration 1～5%, reactive sputtering Zn-Mg alloys target or sputter Mg subsequently
xZn
1-xThe O ceramic target prepares Mg
xZn
1-xO film 1～3nm is as barrier layer B, and final reaction sputter Zn target prepares oxygen-containing vacancy (O
v) ZnO film modulating layer M2～6nm, so just finish the preparation of the modulation doping transparent conductive oxide of one-period.Repeat above-mentioned steps 20～160 times, can get layer modulation-doped ZnO-MgZnO transparent conductive oxide film.
Embodiment two:
Molecular beam epitaxy:
(Knudson) chamber was exerted once by gram by molecular beam epitaxy (MBE) system and the radio frequency plasma chamber constitutes.Load onto Zn (7N), Mg (4N), Al (4N) in the Knudson chamber, radio frequency plasma chamber configuration O
2(5N), base vacuum 5 * 10 in the MBE growth room
-8Pa, operating air pressure are 8 * 10
-5Pa, Zn, Mg, Al molecular beam are equivalent to 2 * 10
-4Pa, 2 * 10
-6～1 * 10
-5Pa handles substrate S earlier before the deposition, as Sapphire Substrate, carry out heat treatment in 750 ℃, 10 minutes earlier, 500 ℃ again, 10 minutes plasma resonances are then at 570 ℃ of deposit ZnO resilient coating B1 (10～20nm), oxygen flow is 0.9sccm, and the Zn molecular beam is equivalent to (BEP) 3 * 10
-6Torr, the growth rate of ZnO is controlled by oxygen flow.Same temperature under the same Zn molecular beam, (is equivalent to 1 * 10 by changing the Mg molecular beam
-8～7 * 10
-8Torr) and the Al molecular beam (be equivalent to 1 * 10
-9～8 * 10
-9Torr), change Mg content (10%～33%) and Al and mix (1～5%), obtain Mg
xZn
1-xO:Al film D (2～6nm).The same condition deposits Mg
xZn
1-xO film B (1～3nm), last, change oxygen flow 0.2～0.4sccm, preparation ZnO:O
vFilm M (2～6nm), finish the preparation of the transparent conductive oxide of one-period.Repeat above-mentioned steps 20～160 times, can get layer modulation-doped ZnO-MgZnO transparent conductive oxide film.
Embodiment three:
Pulsed laser deposition: the KrF excimer laser is made excitaton source, repetition rate 1Hz, between target and substrate S apart from 4cm, laser pulse energy metric density 1～3J/cm
2, growth room's background air pressure 10
-4Pa, and laser radiation ZnO target (99.999%) growth ZnO resilient coating B1 (10～20nm), about 400 ℃ of temperature, oxygen is pressed 2Pa, laser radiation Mg subsequently
xZn
1-xO:Al target growth Mg
xZn
1-xO:Al film D (2～6nm), about 500 ℃ of temperature, oxygen is pressed 5～15Pa, and erosion Mg reburns
xZn
1-xO ceramic target deposition Mg
xZn
1-x(1～3nm), condition is with the doping situation, the ZnO ceramic target of ablating at last ZnO:O for O B
vFilm M (2～6nm), about 400 ℃ of temperature, oxygen is pressed 1Pa.So just finish the preparation of the transparent conductive oxide of one-period.Repeat above-mentioned steps 20～160 times, can get layer modulation-doped ZnO-MgZnO transparent conductive oxide film.
Claims (4)
1. a layer modulation-doped transparent conductive oxide film is applicable to electrooptical device or transparent electronics, and its structure is substrate/ZnO resilient coating/Mg
xZn
1-xO:Al/Mg
xZn
1-xO/ZnO:O
v/ Mg
xZn
1-xO:Al/Mg
xZn
1-xO/ZnO:O
v..., it is characterized in that behind substrate, adding resilient coating ZnO and layer modulation-doped layer, modulate-doped layer is by the Mg of broad energy gap
xZn
1-xO doped layer, unadulterated Mg
xZn
1-xThe ZnO:O of the O barrier layer and the narrower energy gap that do not mix
vModulating layer is formed.
2. layer modulation-doped transparent conductive oxide film according to claim 1 is characterized in that the modulate-doped layer cycle is 20～160, the thickness 2～6nm of doped layer and modulating layer, the thickness 1～3nm on barrier layer, buffer layer thickness 10～20nm.
3. layer modulation-doped transparent conductive oxide film according to claim 2 is characterized in that in the modulate-doped layer content 0.1≤x≤0.33 of Mg in the doped layer and barrier layer.
4. layer modulation-doped transparent conductive oxide film according to claim 3 is characterized in that the Al concentration of dopant atoms is less than 5% in the doped layer.
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| CN105742190A (en) * | 2016-05-09 | 2016-07-06 | 常州工学院 | Preparation method of ZnO-based asymmetric quantum well tunneling homogeneous p-n diode |
| KR20220156821A (en) * | 2020-03-19 | 2022-11-28 | 닛토덴코 가부시키가이샤 | transparent conductive film |
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