CN1797709A - Zinc oxide film on silicon substrate and preparation method - Google Patents
Zinc oxide film on silicon substrate and preparation method Download PDFInfo
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- CN1797709A CN1797709A CN 200410065875 CN200410065875A CN1797709A CN 1797709 A CN1797709 A CN 1797709A CN 200410065875 CN200410065875 CN 200410065875 CN 200410065875 A CN200410065875 A CN 200410065875A CN 1797709 A CN1797709 A CN 1797709A
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Abstract
The invention is related to material of semiconductive thin film, especially to semiconductor material in broad forbidden band. The material includes substrate, transition layer and ZnO epitaxial layer. The transition layer is SiC film layer formed on Si baseplate. Thickness of the SiC film is 0.005-3 micro. Preparing method includes following steps: cleaning Si baseplate, preparing SiC transition layer on cleaned baseplate with surface oxygen being removed by using silicane and propane as reaction source under hydrogen atmosphere, 2000 Pa vacuum pressure, and 1200-1400 deg.C. Reducing lattice defect caused by lattice mismatch and thermal co mismatch, the invention raises quality of ZnO thin film on Si substrate. Features are: high breakdown field strength of SiC, mature epitaxial technique, lower cost, raised degree of crystallinity of ZnO thin film, and enhanced luminous intensity of ultraviolet.
Description
Technical field:
The present invention relates to semiconductor film material, particularly semiconductor material with wide forbidden band.
Background technology:
Third generation semiconductor material with wide forbidden band ZnO is another the later ultra-violet light-emitting material of GaN that continues, and in the photoelectric information functional field great application prospect is arranged.At present, at zno-based sheet and Al
2O
3, ScAlMgO
4On the substrate, realized the preparation of single crystal ZnO film.Si is the comparatively cheap backing material of a kind of cost, and purposes is very extensive.If can utilize the Si substrate to come the extension ZnO film, can reduce cost on the one hand, be beneficial to industrialized development; Simultaneously, also will help synthesizing, develop the zno-based photoelectric device more widely with the photoelectricity of ZnO device.Yet owing to have bigger lattice mismatch and thermal mismatching between ZnO and the Si substrate, direct extension goes out high-quality ZnO monocrystal thin films on the Si substrate so be difficult in.The lattice constant of SiC and thermal coefficient of expansion are similar to ZnO, therefore utilize the backing material of SiC as ZnO film, and technical realization is more or less freely." Japanese Journal of Applied physics Part 1-regular papersshort notes ﹠amp in 2004; Review papers, 43 (2004) p1114-1117 " reported the result of preparation ZnO film on the 6H-SiC monocrystal chip.But the SiC monocrystalline costs an arm and a leg, and is not suitable for the industrialized development of ZnO.In addition, the way that transition zone is set between ZnO and Si is also arranged, for example, in " Journal of the Korean physical society32 (1998) S1741-S1743 ", reported material, be mainly used in the acoustic duct device with ZnO/AlN/Si structure.Because AlN is similar to insulator, is difficult to photoelectric device.So far yet there are no report and adopt SiC to do on Si, the grow technology of ZnO of transition zone.
Summary of the invention:
The objective of the invention is to, overcome Si and ZnO lattice mismatch issue, select suitable material, be used to prepare high-quality ZnO film, reduce preparation cost simultaneously, make its industrialized development as transition zone.
Purpose of the present invention realizes in the following manner.
Zinc-oxide film with silicon substrate of the present invention comprises substrate, transition zone and ZnO epitaxial loayer, it is characterized in that, described transition zone is to utilize silane and the propane SiC rete that growth forms as reaction source on the Si substrate, and this layer thickness is the 0.005-3 micron.
Preparation method with zinc-oxide film of silicon substrate of the present invention, comprise and clean Si substrate, preparation SiC transition zone and preparation ZnO film, it is characterized in that, described preparation SiC transition zone is on the Si substrate of removing surperficial oxygen, utilize silane and propane as reaction source, nitrogen atmosphere, pressure greater than 2000 handkerchief vacuum, 1200-1400 ℃ temperature environment in growth form the SiC rete, its growth time is 10-250 minute, C
3H
8Flow is a 3-30 standard ml/min, SiH
4Flow is a 10-200 standard ml/min.
Its concrete preparation process is:
(1) cleans the Si substrate, and put into the preset vacuum chamber of MOCVD system;
(2) preparation SiC transition zone.Si substrate in the preset vacuum chamber is sent into the pyroreaction chamber by sample feeding mechanism, remove the oxygen on Si surface with conventional method, utilize silane and propane as reaction source then, form the SiC rete at nitrogen atmosphere, pressure greater than the indoor growth of the pyroreaction of 2000 handkerchief vacuum, 1200-1400 ℃ temperature environment, regulate control growing time and C according to required thicknesses of layers
3H
8And SiH
4Flow.
(3) preparation ZnO film.The substrate that utilizes sample feeding mechanism will have the SiC transition zone moves into the ZnO reative cell from the pyroreaction chamber, under blanket of nitrogen, utilize CO
2With diethyl zinc (DEZ) as microsclerly becoming in reaction source next life, its technical conditions are identical with the prior art of growth ZnO on the Si substrate with operating procedure.
The crystalline quality of SiC thin layer is mainly determined by temperature.Temperature is high more, and the crystalline quality of SiC film is high more, and simultaneously, the thickness of SiC film also plays certain influence to crystallization.When film thickness improved, crystalline quality improved.In the process of preparation SiC transition zone, the C when changing growth
3H
8And SiH
4Flow, and growth time can obtain the SiC film of different-thickness and different crystalline qualities.If increase C
3H
8Or SiH
4Flow, perhaps prolong the reaction time all can make thickness of sample obtain increasing, crystalline quality also can obtain corresponding raising.
In the process of preparation ZnO film, change N
2Total flow, and growth time can obtain the film of different-thickness and different surfaces pattern.If increase N
2Total flow can be accelerated reaction rate, and simultaneously, it is more smooth that the surface also can become.
Zinc-oxide film with silicon substrate of the present invention utilizes SiC conduct transition zone between the two, has reduced the lattice defect that is caused by lattice mismatch and coefficient of thermal expansion mismatch well, thereby improved the crystalline quality of the ZnO film for preparing on the Si base; Utilize the high advantage of SiC disruptive field intensity simultaneously, be expected to open up the novel photoelectric material of zno-based.Because the epitaxy technology of SiC/Si material is comparatively ripe, cost is relatively cheap, therefore, and extension ZnO film easy realization of industrialization on this basis.Experimental result shows that the ZnO/SiC/Si film is greatly improved than the crystallization degree of the ZnO film that direct extension on the Si substrate goes out, and ultra-violet light-emitting intensity also strengthens greatly.
Preparation method with zinc-oxide film of silicon substrate of the present invention uses the SiC rete as buffer layer material on the Si substrate first, makes high-quality ZnO film on the Si substrate.Two step extensions all can be utilized existing MOCVD growing technology, and are comparatively ripe, hold and control overall process easily, help guaranteeing product quality.Guaranteeing that sample is not subjected under the air-polluting situation, last epitaxial sic of Si and SiC go up the two one-step growth processes of extension ZnO and can finish in different system respectively, if but can in same system with a plurality of reative cells, finish preparation, the not only pollution that can avoid sample between different system, may be subjected in the transmission course, also can overcome simultaneously the cross pollution that the growth different materials is subjected in same reative cell, this is with the quality of more favourable raising semiconductive thin film.
Description of drawings
Fig. 1 is the schematic diagram with ZnO/SiC/Si structure of the present invention.
Fig. 2 is the twin crystal X-ray diffraction and the swing curve figure thereof of the ZnO film of following embodiment 3 gained.
Fig. 3 is the ZnO film of following embodiment 3 gained and the ZnO film photoluminescence spectrum comparison diagram at room temperature that does not have the SiC transition zone.
Referring to Fig. 1, the 1st, substrate Si, the 2nd, SiC transition zone, the 3rd, ZnO epitaxial loayer.
Fig. 2 is the result to the X ray double crystal diffraction test of gained ZnO film among the following embodiment 3.When the SiC transition zone waves half-breadth when reaching 0.63 °, utilize the diffraction maximum of the ZnO film of above-mentioned condition preparation only to have (002) and (004) orientation thereon, the half-breadth of waving that its (002) is orientated has reached 1.11 °.If increase the thickness of ZnO film, be expected to obtain the better ZnO film of crystallization.
Fig. 3 is the ZnO film and the ZnO film photoluminescence spectrum comparative result at room temperature that does not have the SiC transition zone to following embodiment 3 gained.As seen from the figure, the luminous obvious enhancing of sample of SiC layer is arranged, compare the ZnO film of no SiC transition zone, its luminous intensity has increased about 1 order of magnitude.
Embodiment:
Be further described below by embodiment and accompanying drawing.
1,2 inches Si (111) substrate is finished cleaning and put into MOCVD preset vacuum chamber by previously described step.The cleaning of Si substrate.Si substrate size is 2 inches.Use carbon tetrachloride, the ultrasonic cleaning 10 minutes successively of toluene, acetone, absolute ethyl alcohol is taken out and is rinsed well with deionized water; At H
2O: H
2O
2: H
2SO
4=6: soaked 10 minutes in 1: 1 the mixed liquor, take out and rinse well with deionized water; Utilize 50% HF to soak 2 minutes, take out and rinse well with deionized water; With the N that does
2Put into the preset vacuum chamber after drying up.
2, the Si substrate is utilized sample feeding mechanism, send into the SiC reative cell, open the molecular pump pumping high vacuum then.When vacuum degree reaches 6 * 10
-3Handkerchief, the closure molecule pump directly uses the Lodz pump to keep vacuum in the reaction equation, and feeds H
2, flow 1.5 standard Liter Per Minutes (SL).Behind the system stability, begin to heat up with 40 ℃/min speed from room temperature, when temperature arrives 1200 ℃, constant temperature 20 minutes.Naturally cool to 700 ℃ then, after the temperature constant, feed the propane of 3.5 standard milliliter per minutes (sccm), and be warmed up to 1250 ℃ with 40 ℃/min speed, vacuum degree remains on 2000 handkerchiefs.Temperature arrives the back and finishes growth at once, and the off-response source is at H
2Protection obtains the SiC rete after the cooling down.
3, the preparation of ZnO film.The substrate that will have the SiC transition zone utilizes sample feeding mechanism to move into the ZnO chamber from the SiC reative cell, prepares the extension of ZnO film.Open molecular pump, pumping high vacuum.When vacuum degree reaches 4 * 10
-3Handkerchief, the closure molecule pump directly uses the Lodz pump to keep vacuum in the reaction equation, and feeds N
2, flow 0.86SL.Behind the system stability, begin to heat up.Growth temperature is 600 ℃.After the temperature constant, feed CO respectively
2And DEZ, flow is respectively 60sccm and 7.0sccm, and the pipelines different from two-way feed reative cell.DEZ is by N
2Carry, the source temperature control is at-10 ℃.Bloat next DEZ steam again through one road N from the bubbling bottle
2Quicken E
5Flow is 50sccm.The pressure of reative cell is 130 handkerchiefs during growth.Finish growth after 60 minutes.After sample takes out, 700 ℃ of annealing after 1 hour in air again.After testing, this SiC transition zone is thinner, and thickness is 35nm, twin crystal X-ray diffraction swing curve half-breadth 1.9 degree of its (111) orientation; By its ZnO film for preparing (002) orientation twin crystal X-ray diffraction swing curve half-breadth 2.7 degree.
1,2 inches Si substrates are finished cleaning and put into the preset vacuum chamber by embodiment 1 described step.
2, the Si substrate is utilized sample feeding mechanism, import the SiC reative cell into, open the molecular pump pumping high vacuum then.When vacuum degree reaches 6 * 10
-3Handkerchief, the closure molecule pump directly uses the Lodz pump to keep vacuum in the reaction equation, and feeds H
2, flow 1.5SL.Behind the system stability, begin to heat up with 40 ℃/min speed from room temperature, when temperature arrives 1200 ℃, constant temperature 20 minutes.Naturally cool to 700 ℃ then, after the temperature constant, feed the propane of 3.5sccm, and be rapidly heated 1375 ℃, vacuum degree remains on 2000 handkerchiefs.Finish growth ending after 90 minutes, the off-response source is at H
2Protection cooling down.
3, the preparation of ZnO film layer is with embodiment 1.
After testing, the SiC transition region thickness that obtains is 90nm, its (111) orientation twin crystal X-ray diffraction swing curve half-breadth 1.32 degree; By its ZnO film for preparing (002) orientation twin crystal X-ray diffraction swing curve half-breadth 1.48 degree.
1,2 inches Si (111) substrate is finished cleaning and put into the preset vacuum chamber by embodiment 1 described step.
2, the Si substrate is utilized sample feeding mechanism, import the SiC reative cell into, open the molecular pump pumping high vacuum then.When vacuum degree reaches 6 * 10
-3Handkerchief, the closure molecule pump directly uses the Lodz pump to keep vacuum in the reaction equation, and feeds H
2, flow 1.5SL.Behind the system stability, begin to heat up with 40 ℃/min speed from room temperature, when temperature arrives 1200 ℃, constant temperature 20 minutes.Naturally cool to 700 ℃ then, after the temperature constant, feed the propane of 3.5sccm, and be rapidly heated 1375 ℃, feed the silane of 20sccm 5% after 5 minutes, the growth of beginning SiC transition zone.The vacuum degree of this moment remains on 2000 handkerchiefs, finishes growth ending after 90 minutes, and the off-response source is at H
2Protection cooling down.
3, the preparation of ZnO film layer is with embodiment 1.
After testing, the SiC transition region thickness that obtains is 900nm, its (111) orientation twin crystal X-ray diffraction swing curve half-breadth 0.67 degree; By its ZnO twin crystal (002) for preparing orientation X-ray diffraction swing curve half-breadth 1.11 degree.
Claims (2)
1. the zinc-oxide film with silicon substrate comprises substrate, transition zone and ZnO epitaxial loayer, it is characterized in that, described transition zone is to utilize silane and the propane SiC rete that growth forms as reaction source on the Si substrate, and this layer thickness is the 0.005-3 micron.
2. preparation method with zinc-oxide film of silicon substrate, comprise and clean Si substrate, preparation SiC transition zone and preparation ZnO film, it is characterized in that, described preparation SiC transition zone is on the Si substrate of removing surperficial oxygen, utilize silane and propane as reaction source, nitrogen atmosphere, pressure greater than 2000 handkerchief vacuum, 1200-1400 ℃ temperature environment in growth form the SiC rete, its growth time is 10 minutes to 250 minutes, C
3H
8Flow is a 3-30 standard ml/min, SiH
4Flow is a 10-200 standard ml/min.
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|---|---|---|---|
| CN 200410065875 CN1797709A (en) | 2004-12-21 | 2004-12-21 | Zinc oxide film on silicon substrate and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100514562C (en) * | 2006-09-18 | 2009-07-15 | 中国科学院半导体研究所 | Making method for large-area 3C-SiC thin film of MEMS part |
| CN100546017C (en) * | 2006-12-28 | 2009-09-30 | 中国科学院半导体研究所 | A kind of silicon based compliant substrate material that is used for zinc oxide epitaxial film growth |
| CN101494269B (en) * | 2008-12-18 | 2010-05-12 | 济南大学 | Method for preparing zinc oxide film using buffer layer |
-
2004
- 2004-12-21 CN CN 200410065875 patent/CN1797709A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100514562C (en) * | 2006-09-18 | 2009-07-15 | 中国科学院半导体研究所 | Making method for large-area 3C-SiC thin film of MEMS part |
| CN100546017C (en) * | 2006-12-28 | 2009-09-30 | 中国科学院半导体研究所 | A kind of silicon based compliant substrate material that is used for zinc oxide epitaxial film growth |
| CN101494269B (en) * | 2008-12-18 | 2010-05-12 | 济南大学 | Method for preparing zinc oxide film using buffer layer |
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