CN101625971B - Method for etching class-III nitride by using photo-assisted oxidation wet method - Google Patents
Method for etching class-III nitride by using photo-assisted oxidation wet method Download PDFInfo
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- CN101625971B CN101625971B CN2008101164145A CN200810116414A CN101625971B CN 101625971 B CN101625971 B CN 101625971B CN 2008101164145 A CN2008101164145 A CN 2008101164145A CN 200810116414 A CN200810116414 A CN 200810116414A CN 101625971 B CN101625971 B CN 101625971B
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Abstract
The invention discloses a method for etching class-III nitride by using a photo-assisted oxidation wet method, which is characterized by comprising the following steps: step 1, preparing an ultraviolet light masking layer with patterns on the surface of the class-III nitride by using a standard photo-etching process; step 2, placing the class-III nitride of which the surface is provided with the ultraviolet light masking layer with the patterns under high-energy ultraviolet light to be exposed so as to oxidize the exposed class-III nitride with the patterns under the assistance of the ultraviolet light to generate a metal oxide; step 3, removing the masking layer; and step 4, putting a sample of the exposed class-III nitride in acid or alkali solution so that the generated metal oxide is fully eroded to form an etching step with the patterns to finish the process for etching the class-III nitride by the wet method.
Description
Technical field
The invention belongs to the semiconductor process techniques field, definite a kind of method of utilizing photo-assisted oxidation wet etching III group-III nitride (comprising GaN, AlN, InN and ternary thereof or multi-element compounds) of saying so.
Background technology
Characteristics such as the III group-III nitride (comprising GaN, AlN, InN and ternary thereof or multi-element compounds) with direct band gap is wide because of its spectral coverage, the saturated migration velocity height of electronics, thermal conductance and good thermal stability more and more are subjected to people's attention at opto-electronic device and high-frequency high-power devices field.In most devices manufacture craft process, etching is inevitable operation.Etching is exactly to produce step such as various patterns such as point, spot, lines, hole, grooves at semiconductor surface, it is a requisite technical process of developing high-tech electronic device, to semiconductor surface clean, microfabrication, circuit design and to the structure of research interface important effect is arranged.Semiconductor etching is divided into physical etchings and chemical etching according to the etching principle.So-called physical etchings also claims dry etching sometimes, mainly contains inductively coupled plasma (ICP) etching, reactive ion beam etching (RIBE) (RIE), electron cyclotron resonance (ECR) plasma etching, chemically assisted ion beam etching (CAIBE) and magnetic control reactive ion etching (MIE) etc. at present.The equipment of dry etching is generally all bulky, cost an arm and a leg, and vacuum degree is required to operate also more complicated, and will use toxic gas in many methods than higher, brings a lot of difficulties to production.So-called chemical etching is commonly called as wet etching, utilizes chemical reagent to contact with semiconductor surface exactly and reacts.The equipment of wet etching is simple, and is easy to operate, and toxicity is little, low to material damage, is well replenishing of dry etching.Regrettably have very high thermal stability and chemical stability under the III group-III nitride nature situation, under the lower temperature (23 ~ 80 ℃), adopt general chemical solution etch rate to be almost 0.Most of technologies of III group-III nitride are the using plasma dry etchings at present, but dry etching exists on producing a lot of difficulties, also there are other a lot of defectives, the general energy of the ion that is adopted such as dry etching is all very high, can induce one the inevitably damage of ion etching causes adverse effect to the electric leakage of device or stability etc., dry etching is difficult to obtain smooth etching table top in addition, and smooth chamber face is the necessary condition of laser works.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing photo-assisted oxidation wet etching III group-III nitride, this method is utilized ultraviolet light to assist cleverly and is made nitride generation oxidation, and suitable acid or the alkaline solution of the corrosion resistance different choice of metal oxide and nitride can obtain very high selection ratio, thereby the zone of oxidation is removed, form the etching step that has certain pattern.The equipment that this method is used is simple, easy to operate and toxicity is little, the more important thing is that this method is little to the damage that material surface causes, and the table top that etches simultaneously is more smooth.
The invention provides a kind of method of utilizing photo-assisted oxidation wet etching III group-III nitride, it is characterized in that, comprise the steps:
Step 1: utilize the photoetching process of standard to make figuratum ultraviolet light masking layer on III group-III nitride surface;
Step 2: the III group-III nitride of making figuratum ultraviolet light masking layer on the surface is placed exposure under the high energy ultraviolet light, and the III group-III nitride that makes the exposure with pattern generates metal oxide in the auxiliary generation down of ultraviolet light oxidation;
Step 3: remove masking layer;
Step 4: the sample of the III group-III nitride after will exposing is placed in acid or the alkaline solution, and the metal oxide that generates is eroded fully, forms the etching step that has pattern, finishes the technology of wet etching III group-III nitride.
The material of wherein said III group-III nitride is: GaN, AlN or InN or ternary or the multi-element compounds be made up of them.
Wherein said ultraviolet photoetching is to control the thickness that generates metal oxide by time for exposure and ultraviolet ray intensity, thus the degree of depth of control etching.
The invention provides a kind of method of utilizing photo-assisted oxidation wet etching III group-III nitride, it is characterized in that, comprise the steps:
Step 1: place the ultraviolet laser of focusing to expose down the III group-III nitride, come mobile example or laser, make the zone that is exposed, generate metal oxide in the auxiliary generation down of Ultra-Violet Laser oxidation by the computer control stepper motor;
Step 2: the III group-III nitride after will exposing places acid or alkaline corrosion liquid, will generate metal oxide and erode fully, forms the etching step that has pattern, finishes the technology of wet etching III group-III nitride.
The material of wherein said III group-III nitride is: GaN, AlN or InN or ternary or the multi-element compounds be made up of them.
The Ultra-Violet Laser exposure of wherein said focusing is to control the thickness that generates metal oxide by time for exposure and laser intensity, thus the degree of depth of control etching.
The invention provides a kind of method of utilizing photo-assisted oxidation wet etching III group-III nitride, it is characterized in that, comprise the steps:
Step 1: the UV laser beam of utilizing spectroscope that ultraviolet laser is sent is divided into the relevant ultraviolet light of two bundles, and the adjustment light path interferes the relevant ultraviolet light beam of two bundles and forms light and dark interference fringe;
Step 2: the III group-III nitride is placed exposure under the coherent laser beam, and the zone that is exposed is at auxiliary oxidation, the generation metal oxide of taking place down of Ultra-Violet Laser;
Step 3: the sample of the III group-III nitride after will exposing places acid or alkaline corrosion liquid, will generate metal oxide and erode fully, forms to have striated etching step, finishes the technology of wet etching III group-III nitride.
The material of wherein said III group-III nitride is: GaN, AlN or InN or ternary or the multi-element compounds be made up of them.
Wherein said coherent laser beam exposure is to control the thickness that generates metal oxide by time for exposure and laser intensity, thus the degree of depth of control etching.
Wherein said coherent laser beam exposure is to control the width and the interval of exposure area by adjusting optical maser wavelength, thus the width of the striated etching step of control etching and interval.
Description of drawings
In order to further specify technology contents of the present invention, below in conjunction with instantiation and accompanying drawing describes in detail as after, wherein:
Fig. 1 (a) makes the ultraviolet light masking layer at III group-III nitride sample surfaces;
Fig. 1 (b) is a ultraviolet photoetching, generates metal oxide;
Fig. 1 (c) is for removing the ultraviolet light masking layer;
Fig. 1 (d) is the erosion removal metal oxide, forms the etching step;
Fig. 2 the present invention proposes masking layer exposure schematic diagram;
The no masking layer laser scan type exposure schematic diagram that Fig. 3 the present invention proposes;
The holographic exposure schematic diagram that Fig. 4 the present invention proposes.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
1 (a), Fig. 1 (b), Fig. 1 (c), Fig. 1 (d) and Fig. 2 are described in detail as follows a kind of first kind of embodiment of the method for photo-assisted oxidation wet etching III group-III nitride of utilizing of the present invention in conjunction with the accompanying drawings.
Step 1: utilize the photoetching process of standard, be manufactured with the ultraviolet light masking layer 11 of certain pattern on the surface of handling III group-III nitride sample 10 to be etched well.Its technical process comprises fired sample, cleans reticle, resist coating, baking photoresist, exposure, development, low temperature plated film, peels off the formation pattern.Specific as follows at first with III group-III nitride sample 10 120 ℃ of down bakings 30 minutes, treat that its cooling back use sol evenning machine is coated with the last layer photoresist uniformly on its surface, toasting down at 90 ℃ subsequently made photoresist have certain rigidity in 20 minutes, utilizing graph exposure equipment is that mask aligner exposes to photoresist, figure transfer to photoresist, is stayed the photoresist with certain figure after the development.Adopt the low temperature filming equipment to cover the not masking layer (as metal) of saturating ultraviolet light of one deck at the sample surfaces that has photoresist.Will form ultraviolet light masking layer 11 at sample surfaces behind the metal-stripping with certain pattern.Masking layer material requirements ultraviolet light can not pass through, and needs technology simply to be convenient to make and to remove, such as metal A l etc.Pattern can be point, line or the bar shaped as shown in Figure 1 of other random geometry according to arts demand.The place that needs etching come out and needs keep the place that is not etched and protect with masking layer 11, shown in Fig. 1 (a);
Step 2: the sample that is manufactured with the ultraviolet light masking layer 11 of certain pattern on the surface is placed exposure under the high energy ultraviolet light, and the III group-III nitride that makes the exposure with certain pattern is at auxiliary oxidation, the generation metal oxide 12 of taking place down of ultraviolet light; Ultraviolet photoetching sees also that Fig. 2 the present invention proposes masking layer exposure schematic diagram.The high energy ultraviolet light can be provided by Xe lamp 21, and the light that scioptics group 20 is sent Xe lamp 21 becomes a branch of uniformly nearly directional light, can reduce like this because the oblique incidence of light causes lateral erosion.In exposure process, control the ultraviolet light intensity by the power of adjusting Xe lamp 21 and the optical parametric of set of lenses 20, cooperate the time for exposure can reach the thickness that the control exposure generates metal oxide 12 simultaneously, and metal oxide 12 is to remove by following etching process, so the thickness of metal oxide 12 degree of depth of etching just.So just can realize certain etching depth by accurate control ultraviolet ray intensity and time for exposure.
Step 3: place the masking layer corrosive liquid to remove masking layer 11 shown in Fig. 1 (c) in sample behind the end exposure.If masking layer 11 can be got rid of simultaneously by the step of following erosion removal metal oxide 12, this step may be incorporated in the following step 4 and carries out simultaneously so;
Step 4: the III group-III nitride sample that masking layer 11 is removed in the back of will exposing is placed in certain density acid or the alkaline solution shown in Fig. 1 (c), requirement makes it not have corrosiveness to the III group-III nitride sample 10 that does not have oxidation simultaneously by optionally quick corroding metal oxide 12 by the control of solution selection and concentration thereof.General acidity or alkaline solution do not have corrosiveness to III group-III nitride 10, and III group-III nitride 10 can be dissolved in acidity or alkaline solution easily by the metal oxide 12 that ultraviolet photoetching generates later on, be that exposed areas is corroded and there is not exposed areas to remain with regard to having formed optionally etching like this, formation has the etching step (shown in Fig. 1 (d)) of certain pattern, finishes the technology of wet etching III group-III nitride.
Because the penetrability of ultraviolet light in general solution is very strong, so the sample of making the ultraviolet light masking layer shown in Fig. 1 (a) can be placed corrosive liquid, require this corrosive liquid that ultraviolet light masking layer 11 is not had corrosiveness, exposure and corrosion just can be carried out simultaneously like this, the metal oxide 12 that ultraviolet photoetching is generated promptly erodes, just can form have certain pattern the etching step shown in Fig. 1 (d).
Embodiment 2:
1 (a), Fig. 1 (b), Fig. 1 (c), Fig. 1 (d) and Fig. 3 are described in detail as follows a kind of second kind of embodiment of the method for photo-assisted oxidation wet etching III group-III nitride of utilizing of the present invention in conjunction with the accompanying drawings.
Step 1, III group-III nitride sample 10 placed the ultraviolet laser 34 times exposure (consulting Fig. 3) of focusing, adjust light path by optical elements sets 35, come mobile example by computer control system 30 accurate control step motors 31, thereby cooperate ultraviolet light switch 33 needing to realize the scan exposure of exposure area.Also stepper motor can be installed on the ultraviolet laser 34 mobile ultraviolet laser 34 or be installed in mobile light path on the optical elements sets 35, needing realize the scan exposure of exposed areas.Ultraviolet laser 34 can be the Ar+ laser of He-Cd laser or frequency multiplication etc.The zone that is exposed is in the auxiliary generation down of Ultra-Violet Laser oxidation, generate metal oxide, control exposure intensity by power and the adjustment optical elements sets 35 of adjusting ultraviolet laser 34, come the translational speed of control step motor 31 just to control laser by computer control system 30 simultaneously and control the thickness that generates metal oxide 12 in the time that a certain zone of sample stops, thus the degree of depth of control etching;
Step 2, the III group-III nitride sample after will exposing are placed in certain density acid or the alkalescence shown in Fig. 1 (c), require by the selection of corrosive liquid 32 and the control of concentration thereof, make it not have corrosiveness to the III group-III nitride sample 10 that does not have oxidation simultaneously by optionally quick corroding metal oxide 12.General acidity or alkaline solution do not have corrosiveness to III group-III nitride 10, and III group-III nitride 10 can be dissolved in acidity or alkaline solution easily by the metal oxide 12 that ultraviolet photoetching generates later on, be that exposed areas is corroded and there is not exposed areas to remain with regard to having formed optionally etching like this, formation has the etching step (shown in Fig. 1 (d)) of certain pattern, finishes the technology of wet etching III group-III nitride.
Because the penetrability of ultraviolet light in general solution is very strong, so III group-III nitride sample 10 can be placed corrosive liquid 32, exposure and corrosion just can be carried out simultaneously like this, the metal oxide 12 that ultraviolet photoetching is generated promptly erodes, just can form have certain pattern the etching step shown in Fig. 1 (d).
Embodiment 3:
1 (a), Fig. 1 (b), Fig. 1 (c), Fig. 1 (d) and Fig. 4 are described in detail as follows a kind of the third embodiment of the method for photo-assisted oxidation wet etching III group-III nitride of utilizing of the present invention in conjunction with the accompanying drawings.
Step 1, at first adjust light path, be divided into two bundle coherent beams (consulting Fig. 4) after making light that ultraviolet laser 34 sends through speculum 42 and semi-transparent semi-reflecting lens 41.This two bundles coherent beam interferes on III group-III nitride sample 10 surfaces through two speculums, 40 backs respectively, forms light and dark striped.Ultraviolet laser 34 can be the Ar+ laser of He-Cd laser or frequency multiplication etc.
Step 2, III group-III nitride sample 10 expose under light and dark ultraviolet light interference fringe, it is that bright strip-area is in the auxiliary generation down of Ultra-Violet Laser oxidation that ultraviolet light is strengthened, generate metal oxide, it is that oxidation does not then take place in the dark space that ultraviolet light disappears mutually, shown in Fig. 1 (c).By adjusting the power control exposure intensity of ultraviolet laser 34, control the time for exposure simultaneously, control the thickness that generates metal oxide 12, thus the degree of depth of control etching; Control the width of light and dark striped and width and the interval that the interval is the exposure area by selection optical maser wavelength, thus the width of the striated etching step of control etching and interval.
Step 3, the III group-III nitride sample after will exposing are placed in certain density acid or the alkalescence shown in Fig. 1 (c), require by the selection of corrosive liquid 32 and the control of concentration thereof, make it not have corrosiveness to the III group-III nitride sample 10 that does not have oxidation simultaneously by optionally quick corroding metal oxide 12.General acidity or alkaline solution do not have corrosiveness to III group-III nitride 10, and III group-III nitride 10 can be dissolved in acidity or alkaline solution easily by the metal oxide 12 that ultraviolet photoetching generates later on, be that exposed areas is corroded and there is not exposed areas to remain with regard to having formed optionally etching like this, formation has the etching step (shown in Fig. 1 (d)) of certain pattern, finishes the technology of wet etching III group-III nitride.
Because the penetrability of ultraviolet light in general solution is very strong, so III group-III nitride sample 10 can be placed corrosive liquid 32, exposure and corrosion just can be carried out simultaneously like this, the metal oxide 12 that ultraviolet photoetching is generated promptly erodes, just can form have certain pattern the etching step shown in Fig. 1 (d).
Claims (10)
1. a method of utilizing photo-assisted oxidation wet etching III group-III nitride is characterized in that, comprises the steps:
Step 1: utilize the photoetching process of standard to make figuratum ultraviolet light masking layer on III group-III nitride surface;
Step 2: the III group-III nitride of making figuratum ultraviolet light masking layer on the surface is placed exposure under the high energy ultraviolet light, and the III group-III nitride that makes the exposure with pattern generates metal oxide in the auxiliary generation down of ultraviolet light oxidation;
Step 3: remove masking layer;
Step 4: the sample of the III group-III nitride after will exposing is placed in acid or the alkaline solution, and the metal oxide that generates is eroded fully, forms the etching step that has pattern, finishes the technology of wet etching III group-III nitride.
2. the method for utilizing photo-assisted oxidation wet etching III group-III nitride according to claim 1 is characterized in that the material of wherein said III group-III nitride is: GaN, AlN or InN or ternary or other multi-element compounds be made up of them.
3. the method for utilizing photo-assisted oxidation wet etching III group-III nitride according to claim 1, it is characterized in that, wherein said ultraviolet photoetching is to control the thickness that generates metal oxide by time for exposure and ultraviolet ray intensity, thus the degree of depth of control etching.
4. a method of utilizing photo-assisted oxidation wet etching III group-III nitride is characterized in that, comprises the steps:
Step 1: place the ultraviolet laser of focusing to expose down the III group-III nitride, come mobile example or laser, make the zone that is exposed, generate metal oxide in the auxiliary generation down of Ultra-Violet Laser oxidation by the computer control stepper motor;
Step 2: the III group-III nitride after will exposing places acid or alkaline corrosion liquid, will generate metal oxide and erode fully, forms the etching step that has pattern, finishes the technology of wet etching III group-III nitride.
5. the method for utilizing photo-assisted oxidation wet etching III group-III nitride according to claim 4 is characterized in that the material of wherein said III group-III nitride is: GaN, AlN or InN or ternary or other multi-element compounds be made up of them.
6. the method for utilizing photo-assisted oxidation wet etching III group-III nitride according to claim 4, it is characterized in that, the Ultra-Violet Laser exposure of wherein said focusing is to control the thickness that generates metal oxide by time for exposure and laser intensity, thus the degree of depth of control etching.
7. a method of utilizing photo-assisted oxidation wet etching III group-III nitride is characterized in that, comprises the steps:
Step 1: the UV laser beam of utilizing spectroscope that ultraviolet laser is sent is divided into the relevant ultraviolet light of two bundles, and the adjustment light path interferes the relevant ultraviolet light beam of two bundles and forms light and dark interference fringe;
Step 2: the III group-III nitride is placed exposure under the coherent laser beam, and the zone that is exposed is at auxiliary oxidation, the generation metal oxide of taking place down of Ultra-Violet Laser;
Step 3: the sample of the III group-III nitride after will exposing places acid or alkaline corrosion liquid, will generate metal oxide and erode fully, forms to have striated etching step, finishes the technology of wet etching III group-III nitride.
8. the method for utilizing photo-assisted oxidation wet etching III group-III nitride according to claim 7 is characterized in that the material of wherein said III group-III nitride is: GaN, AlN or InN or ternary or other multi-element compounds be made up of them.
9. the method for utilizing photo-assisted oxidation wet etching III group-III nitride according to claim 7, it is characterized in that, wherein said coherent laser beam exposure is to control the thickness that generates metal oxide by time for exposure and laser intensity, thus the degree of depth of control etching.
10. the method for utilizing photo-assisted oxidation wet etching III group-III nitride according to claim 7, it is characterized in that, wherein said coherent laser beam exposure, be to control the width and the interval of exposure area by adjusting optical maser wavelength, thus the width of the striated etching step of control etching and interval.
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| CN102299066B (en) * | 2011-09-22 | 2014-03-26 | 中国电子科技集团公司第十三研究所 | Acid-base alternative wet method for corroding InAlN material |
| CN102856188A (en) * | 2012-08-06 | 2013-01-02 | 北京大学 | Wet etching method for gallium nitride-based device |
| CN103268857B (en) * | 2013-05-13 | 2016-01-13 | 北京大学 | A kind of self-stopping technology lithographic method based on gallium nitride-based material |
| CN103701037B (en) * | 2013-11-27 | 2016-03-23 | 中国科学院半导体研究所 | The manufacture method in face, gallium nitride lasers chamber |
| CN104282548A (en) * | 2014-09-12 | 2015-01-14 | 电子科技大学 | Etching method for III-V-group compound semiconductor materials |
| CN114899096A (en) | 2015-10-14 | 2022-08-12 | 艾克索乔纳斯公司 | Ultra-shallow etch method using neutral beam processing based on gas cluster ion beam technology and articles produced thereby |
| CN105551951A (en) * | 2015-12-18 | 2016-05-04 | 北京代尔夫特电子科技有限公司 | Method for wet etching of group-III nitride |
| TW201939628A (en) * | 2018-03-02 | 2019-10-01 | 美商微材料有限責任公司 | Methods for removing metal oxides |
| CN110459474B (en) * | 2019-06-27 | 2021-04-02 | 惠科股份有限公司 | Manufacturing method of thin film transistor and display device |
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| US6605548B1 (en) * | 1999-06-01 | 2003-08-12 | National Research Council Of Canada | Process for etching gallium nitride compound based semiconductors |
| CN1886827A (en) * | 2003-12-09 | 2006-12-27 | 加利福尼亚大学董事会 | Highly efficient gallium nitride based light emitting diodes via surface roughening |
| CN101103439A (en) * | 2005-01-11 | 2008-01-09 | 美商旭明国际股份有限公司 | Light emitting diodes with improved light extraction by roughening |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6605548B1 (en) * | 1999-06-01 | 2003-08-12 | National Research Council Of Canada | Process for etching gallium nitride compound based semiconductors |
| CN1886827A (en) * | 2003-12-09 | 2006-12-27 | 加利福尼亚大学董事会 | Highly efficient gallium nitride based light emitting diodes via surface roughening |
| CN101103439A (en) * | 2005-01-11 | 2008-01-09 | 美商旭明国际股份有限公司 | Light emitting diodes with improved light extraction by roughening |
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