CN101969023B - Method for making step growth MgxZn1-xO thin film on silicon substrate - Google Patents

Method for making step growth MgxZn1-xO thin film on silicon substrate Download PDF

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CN101969023B
CN101969023B CN2010102445317A CN201010244531A CN101969023B CN 101969023 B CN101969023 B CN 101969023B CN 2010102445317 A CN2010102445317 A CN 2010102445317A CN 201010244531 A CN201010244531 A CN 201010244531A CN 101969023 B CN101969023 B CN 101969023B
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silicon substrate
film
mask
silicon
resist
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CN101969023A (en
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王新
向嵘
李野
王国政
端木庆铎
田景全
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Changchun University of Science and Technology
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Changchun University of Science and Technology
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Abstract

The invention discloses a method for making a step growth MgxZn1-xO thin film on a silicon substrate, which belongs to the technical field of semiconductor photoelectron material manufacturing. In the prior, a buffer layer is introduced onto a silicon substrate, or foreign impurities are introduced into a subsequently grown MgxZn1-xO thin film, or the ratio between Mg and Zn atoms in the MgxZn1-xO thin film is imbalance. While in the invention, before the MgxZn1-xO thin film is grown on the silicon substrate, steps regularly distributed are manufactured on the surface of the silicon substrate, and therefore the surface of the silicon substrate is divided into a top surface and a bottom surface with a height difference of 30 to 200 nanometers in between, and the total area of the top surface is smaller than that of a bottom surface. The method is used for preparing the MgxZn1-xO thin film on the silicon substrate directly.

Description

On silicon substrate, make step growth Mg xZn 1-xThe method of O film
Technical field
The present invention relates to a kind of step growth Mg that on silicon substrate, makes xZn 1-xThe method of O film belongs to Semiconductor Optoeletronic Materials manufacturing technology field.
Background technology
1997, the performance of ZnO film stimulated emission was in the news.Today, ZnO film has become a kind of broad stopband transparent semiconductor photoelectron material.When in ZnO, mixing the Mg element, form Mg xZn 1-xThe O alloy firm can make the energy gap of ZnO film wherein further increase, and has important application in fields such as ultra-violet light-emitting device and ultraviolet detection devices.Application number is 200910066945.2, name is called and " has Al 2O 3The silicon substrate Mg of resilient coating xZn 1-xO film magnetron sputtering preparation method " the Chinese invention patent application disclose one the preparation Mg xZn 1-xThe technical scheme of O film.This scheme adopts magnetically controlled sputter method, earlier at silicon substrate growth Al 2O 3Buffer layer thin film, and then at Al 2O 3Mg grows on the buffer layer thin film xZn 1-xThe O film.The silicon substrate that this method adopted is compared with sapphire in the past, gallium nitride substrate, and price is low, be easy to cutting, and also makes the prepared film device possess and the silicon technology integrated micro of electronics industry and the photoelectron technology prerequisite of compatibility mutually.Also solved directly at silicon substrate growth Mg xZn 1-xThe lattice mismatch phenomenon that the O film occurs causes between substrate and film, existing the problem of very big stress then.Prepare high-quality crystalline state Mg xZn 1-xThe O film, big and even like the poly grains that constitutes film, pattern is smooth, the nothing be full of cracks.In addition, the resilient coating of prior art employing also has GaN, MgO and low temperature ZnO film.
Summary of the invention
Yet still there is its deficiency in prior art, if the resilient coating of introducing is GaN film or Al 2O 3Film can be at the Mg of subsequent growth xZn 1-xIntroduce exogenous impurity in the O film, these impurity can be to Mg xZn 1-xThe structure of O film impacts, thereby has a strong impact on Mg xZn 1-xThe O film comprises the numerous characteristics of optical characteristics, electrology characteristic especially, as cause and be similar to the influence that the semiconductor doping effect is brought; If the resilient coating of introducing is MgO or low temperature ZnO film, Mg atom in the resilient coating or Zn atom can be to the Mg of subsequent growth so xZn 1-xSpread in the O film, cause Mg xZn 1-xMg atom in the O film or the imbalance of Zn atomic ratio.Therefore, in order to overcome the technical problem of prior art because of two aspects introducing resilient coating and bring, keep simultaneously and adopt silicon substrate, we have invented a kind of step growth Mg that on silicon substrate, makes xZn 1-xThe method of O film.
The present invention Mg that on silicon substrate, grows xZn 1-xThe O film is characterized in that, Mg grows on silicon substrate xZn 1-xBefore the O film; Make the step of regular distribution in surface of silicon; Therefore surface of silicon is divided into two kinds of topsheet surface, bottom surface, and topsheet surface, bottom surface height differ 30～200nm, and topsheet surface area sum is less than bottom surface area sum.
Its technique effect of the present invention's method is, does not introduce resilient coating, thereby avoids prior art because of introducing the technical problem of two aspects that resilient coating brought; Keep to adopt silicon substrate simultaneously, thereby with respect to non-silicon substrate, like sapphire, gallium nitride substrate, price is low, be easy to cutting, adopts prepared Mg xZn 1-xThe thin-film device that the O film is made possess with the silicon technology integrated micro of electronics industry and photoelectron technology mutually this advantage of prerequisite of compatibility also be retained.The more important thing is, also solved and do not made direct growth Mg on the silicon substrate of step xZn 1-xThe lattice mismatch phenomenon that the O film occurs causes between substrate and film, existing the problem of very big stress then, and this is because the step of the regular distribution of made has been alleviated said stress greatly from the physics aspect.The measure of making step in surface of silicon also brings a subsidiary effect; That is exactly from film growth theoretically; Nucleation site when these " steps " serve as the film initial growth; The subsequent growth that helps film is because the existence of such nucleation site in a large number also makes film growth rate increase.The Mg for preparing xZn 1-xO film crystalline state quality is high, and is big and evenly like the poly grains that constitutes film, and this point can be by the checking of x x ray diffraction testing result, sees shown in Figure 1ly, and the curve above among the figure is the Mg of the method preparation of adopting the present invention xZn 1-xO film x x ray diffraction detection curve, its diffraction maximum half-peak breadth is merely 0.16 °, and following curve is at the Mg that does not have to grow on the silicon substrate of step xZn 1-xO film x x ray diffraction detection curve, its diffraction maximum half-peak breadth is up to 0.39 °.Adopt the Mg of the present invention's method preparation xZn 1-xThe O film morphology is smooth, do not have be full of cracks, see shown in Figure 2, and at the Mg that does not have to grow on the silicon substrate of step xZn 1-xThe O film then is covered be full of cracks, sees shown in Figure 3.
Description of drawings
Fig. 1 is the Mg that on silicon substrate, grows xZn 1-xO film x x ray diffraction detects figure.Fig. 2 is the Mg that adopts the present invention's method preparation xZn 1-xO film morphology stereoscan photograph.Fig. 3 is the Mg that grows on the silicon substrate of step not having xZn 1-xO film morphology stereoscan photograph.Fig. 4 is the present invention's the silicon substrate sketch map that method adopted.Fig. 5 is that the present invention's method applies resist situation sketch map on silicon substrate.Fig. 6 is method mask film covering version situation sketch map on resist of the present invention.Fig. 7 is that the figure of each non-mask part of method mask of the present invention is the foursquare situation sketch map of fillet.Fig. 8 is that the figure of each non-mask part of method mask of the present invention is circular situation sketch map.Fig. 9 is the present invention's the situation sketch map that the non-mask part of the corresponding mask of method resist part is dissolved, other parts remain.Figure 10 is that the present invention's method is made step situation sketch map on silicon substrate.Figure 11 is the silicon substrate sketch map that the surface of the present invention's method acquisition has the step of regular distribution.Figure 12 is that the surface that the present invention's method obtains has the local schematic top plan view of silicon substrate of the step of regular distribution.Figure 13 is the Mg that grows on the silicon substrate of the present invention's the method step that has regular distribution on the surface xZn 1-xO film situation sketch map, this figure double as is a Figure of abstract.
Embodiment
The present invention's method specifically is achieved in that
Silicon substrate 1 material is a monocrystalline silicon, sees shown in Figure 4ly, and monocrystalline silicon is n type or p type, is perhaps (111) direction of (100) direction; Silicon substrate is carried out strict cleaning, comprise organic washing and inorganic cleaning.
On silicon substrate 1, adopt the method for rotation gluing or spraying to apply one deck resist 2, see shown in Figure 5ly, resist 2 is a photoresist, i.e. photoresist, and perhaps electronic corrosion-resistant both can be a positivity, also can be negativity.
Mask film covering version 3 on resist 2; See shown in Figure 6; Mask 4 figures of mask 3 are consistent with the topsheet surface figure of the surface of silicon of desire making step, and non-mask part 5 figures of mask 3 are consistent with the bottom surface figure of the surface of silicon of desire making step.The figure of each non-mask part 5 is the fillet square, and the length of side is 0.1～100 μ m, sees shown in Figure 7; Perhaps be circular, diameter is 0.1～100 μ m, sees shown in Figure 8.Each non-mask part 5 array distribution, profile phase is seen Fig. 7, shown in Figure 8 apart from 0.1～100 μ m.
Photolithographic exposure resist 2.Wherein, for photoresist, take the optical exposure mode; For electronic corrosion-resistant, then take electron beam or ion beam exposure mode.Remove mask 3 afterwards.
Development resist 2.The part of resist 2 corresponding non-mask parts 5 is dissolved, and other parts remain, and sees shown in Figure 9.
On silicon substrate 1, make step.Adopt the method for corrosion or etching, like one of methods such as wet etching, dry etching or reactive ion etching, silicon substrate 1 surface at processing resist 2 dissolved places; Therefore silicon substrate 1 surface is divided into 7 two kinds of topsheet surface 6, bottom surface; Demonstrate the step of regular distribution, see shown in Figure 10ly, topsheet surface 6, bottom surface 7 highly differ 30～200nm; High 30～the 200nm of step in other words, topsheet surface 6 area sums are less than bottom surface 7 area sums.
Remove resist 2.The employing organic solvent cleans, and removes resist 2, sees shown in Figure 11ly, obtains the silicon substrate 1 that the surface has the step of regular distribution, sees shown in Figure 12.
Growth Mg xZn 1-xThe O film.Clean silicon substrate 1, put into film growth apparatus, as growth substrates.Adopt one of methods such as molecular beam epitaxy, chemical vapour deposition (CVD), sputter coating, pulsed laser deposition, ald preparation Mg xZn 1-xO film 8 is seen shown in Figure 13ly, and wherein the atomic ratio of Mg and Zn is regulated according to concrete equipment voluntarily.
Illustrate the present invention's method below.
Silicon substrate 1 material is a monocrystalline silicon, sees shown in Figure 4ly, and monocrystalline silicon is the n type, is (100) direction; Silicon substrate is carried out strict cleaning:
(a) CCl 4Ultrasonic cleaning 10 minutes, acetone ultrasonic cleaning 10 minutes, deionized water washed 10 minutes repeatedly;
(b) NH 4OH: H 2O 2: H 2O=1: 1: 5,80 ℃, cleaned 10 minutes, deionized water is cleaned;
(c) 0.5%HF soaked 1 minute, and deionized water is cleaned;
(d) HCl: H 2O 2: H 2O=1: 1: 5,80 ℃, cleaned 10 minutes, deionized water is cleaned;
(e) 0.5%HF soaked 1 minute, and deionized water is cleaned.
Dry up silicon substrate 1 with nitrogen at last.
On silicon substrate 1, adopt the method for rotation gluing to apply one deck positive corrosion-resisting agent 2, see shown in Figure 5ly, resist 2 is a photoresist, i.e. photoresist is like PMMA.
Mask film covering version 3 on resist 2; See shown in Figure 6; Mask 4 figures of mask 3 are consistent with the topsheet surface figure of the surface of silicon of desire making step, and non-mask part 5 figures of mask 3 are consistent with the bottom surface figure of the surface of silicon of desire making step.The figure of each non-mask part 5 is the fillet square, and the length of side is 4 μ m.Each non-mask part 5 array distribution, profile phase is seen shown in Figure 7 apart from 2 μ m.
Photolithographic exposure resist 2.Take the optical exposure mode.Remove mask 3 afterwards.
Development resist 2.Developer solution is a KOH solution, concentration 7.5 ‰, and the part of resist 2 corresponding non-mask parts 5 is dissolved, and other parts remain, and see shown in Figure 9.
On silicon substrate 1, make step.Adopt silicon substrate 1 surface at wet etching method processing resist 2 dissolved places; Therefore silicon substrate 1 surface is divided into 7 two kinds of topsheet surface 6, bottom surface; Demonstrate the step of regular distribution, see shown in Figure 10ly, topsheet surface 6, bottom surface 7 highly differ 100nm; The high 100nm of step in other words, topsheet surface 6 area sums are less than bottom surface 7 area sums.
Remove resist 2.The employing organic solvent-acetone cleans, and removes resist 2, sees shown in Figure 11ly, obtains the silicon substrate 1 that the surface has the step of regular distribution, sees shown in Figure 12.
Growth Mg xZn 1-xThe O film.Clean silicon substrate 1, put into molecular beam epitaxial device, as growth substrates.Adopt molecular beam epitaxial method to prepare Mg xZn 1-xO film 8 is seen shown in Figure 13ly, and wherein the atomic ratio of Mg and Zn is regulated according to concrete equipment voluntarily, like Mg 0.1Zn 0.9O.

Claims (5)

1. on silicon substrate, make step growth Mg for one kind xZn 1-xThe method of O film, Mg grows on silicon substrate xZn 1-xThe O film is characterized in that, Mg grows on silicon substrate xZn 1-xBefore the O film; Make the step of regular distribution in surface of silicon; Therefore surface of silicon is divided into two kinds of topsheet surface, bottom surface, and topsheet surface, bottom surface height differ 30～200nm, and topsheet surface area sum is less than bottom surface area sum.
2. growth Mg according to claim 1 xZn 1-xThe method of O film is characterized in that, the process of making the step of regular distribution in surface of silicon is:
A, go up to apply one deck resist (2) at silicon substrate (1);
B, go up mask film covering version (3) at resist (2); Mask (4) figure of mask (3) is consistent with the topsheet surface figure of the surface of silicon of desire making step, and the bottom surface figure of the surface of silicon that non-mask part (5) figure of mask (3) and desire are made step is consistent;
C, photolithographic exposure resist (2);
D, development resist (2), the part of the corresponding non-mask part of resist (2) (5) is dissolved, and other parts remain;
Silicon substrate (1) surface at E, the dissolved place of employing corroding method processing resist (2), therefore silicon substrate (1) surface is divided into (7) two kinds of topsheet surface (6), bottom surface, demonstrates the step of regular distribution.
3. growth Mg according to claim 2 xZn 1-xThe method of O film is characterized in that, the figure of each non-mask part (5) is the fillet square, and the length of side is 0.1～100 μ m, perhaps is circular, and diameter is 0.1～100 μ m; Each non-mask part (5) array distribution, profile phase is apart from 0.1～100 μ m.
4. growth Mg according to claim 2 xZn 1-xThe method of O film is characterized in that, said corroding method is one of wet etching, two kinds of methods of dry etching.
5. growth Mg according to claim 4 xZn 1-xThe method of O film is characterized in that, described dry etching is a reactive ion etching.
CN2010102445317A 2010-08-04 2010-08-04 Method for making step growth MgxZn1-xO thin film on silicon substrate Expired - Fee Related CN101969023B (en)

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CN101210313A (en) * 2006-12-29 2008-07-02 中国科学院长春光学精密机械与物理研究所 Method for growing MgxZn1-xO film by electron-beam evaporation

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