CN102650821B - Method for preparing high-temperature resistant hard photomask - Google Patents
Method for preparing high-temperature resistant hard photomask Download PDFInfo
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- CN102650821B CN102650821B CN201210161659.6A CN201210161659A CN102650821B CN 102650821 B CN102650821 B CN 102650821B CN 201210161659 A CN201210161659 A CN 201210161659A CN 102650821 B CN102650821 B CN 102650821B
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Abstract
The invention belongs to the technical field of micro-electronics and particularly provides a method for preparing a high-temperature resistant hard photomask. The high-temperature resistant hard photomask is made of zinc oxide and is particularly prepared in the way that positive photoresist is used to transfer patterns on a substrate through the traditional photolithography, then a zinc oxide film is deposited under ambient temperature, and after the photoresist and the zinc oxide film thereon are removed, patterns contrary to those of the photoresist are left. On that basis, various high-temperature growing materials can be deposited under high temperature as required; and finally, the zinc oxide and material thereon can be removed by low-concentration acid which can corrode zinc oxide quickly but hardly influences the deposited materials, and the purpose that various pattern deposition material structures are formed on the substrate can be achieved at last.
Description
Technical field
The invention belongs to the microelectronic manufacturing technology field, be specifically related to a kind of high temperature resistant hard mask plate preparation method.
Background technology
Photoetching technique is the basis of electronics industry as the ic manufacturing technology of microelectric technique core, and the speed that its development is upgraded is that other industries can't be reached.In integrated circuit fabrication process, photoetching is its critical process.Photoresist is coated on semiconductor, conductor and insulator, and the part stayed after exposure imaging shields to bottom, then adopts ultra-clean and high pure chemical reagent to carry out etching, thereby completed, mask plate patterns is transferred to the figure transfer process on bottom.The manufacture of an IC generally need to just can complete through more than 10 figure transfer processes, and photoresist and etching technique are to realize the key of integrated circuit Micrometer-Nanometer Processing Technology.
Along with microelectric technique further develops, new material, new technology are introduced into the integrated circuit manufacture in succession, such as the non-volatile ferroelectric memory manufacture of a new generation, micro mechanical system etc.These new materials much all require film growth under special technique, particularly hot environment.Traditional lithography mask version is divided into positive photoresist and negative photoresist, but they are all organism, have restricted so to a certain extent new construction, the practical application of new technology.Therefore under hot environment, transition diagram has become an extremely urgent technical matters.
It is high that zinc oxide material has fusing point (1975 ℃), very easily by watery hydrochloric acid, phosphoric acid,diluted, removed, and in advantages such as temperature (1000 ℃) are stable and cheap, these advantages make zinc paste become a kind of desirable hot environment and shift mask plate with figure.
Summary of the invention
The object of the invention is to the limitation that can not use in hot environment for traditional photoresist, propose a kind of high temperature resistant hard mask plate preparation method.
A kind of high temperature resistant hard mask plate preparation method that the present invention proposes, be embodied in and on substrate, utilize conventional lithographic techniques to use the positive photoresist transition diagram, then deposit one deck zinc-oxide film under room temperature, remove photoresist and on the zinc oxide films rete on substrate, stay the figure contrary with photoresist.On this basis, various high growth temperature materials of (below 1000 ℃) deposit as required at high temperature, finally by quick corrosion oxidation zinc but the dilute concentration acid that institute's deposition materials impact is ignored remove zinc paste and on material, finally realize the various deposited in pattern material structures of formation on substrate.Its concrete steps are as follows:
, on substrate, prepare the positive photoresist figure (this figure should with finally prepare figure consistent) of certain thickness (as 200 nanometers to 5 micron) by photoetching technique;
(2), residual with the photoresist in the positive photoresist zone of photolithographic exposure and the removal of developing on source of oxygen removal substrate in the ion etching machine;
, in deposition apparatus, deposit certain thickness under room temperature on the substrate with the positive photoresist figure (as 50 nanometers to 500 nanometers) zinc oxide films rete, obtain print;
, by above-mentioned print immerse positive photoresist on acetone soln ultrasonic removal substrate and on the zinc oxide films rete, then with absolute ethyl alcohol, clean up, and dry up with nitrogen;
(5), residual with the photoresist of non-oxide zinc covering place on source of oxygen removal print substrate in the ion etching machine, subsequently print in quick anneal oven, under oxygen atmosphere, 500 ℃ to 1000 ℃ high temperature, short annealing is 5 minutes to 30 minutes, make zinc-oxide film by the amorphous crystal structure that is changed to, now on substrate, the zinc oxide films rete is high temperature resistant hard mask plate;
, in deposition apparatus, application zinc paste hard mask plate, deposit certain thickness in 200 ℃ to 1000 ℃ temperature environments (as 10 nanometers to 500 nanometers) high growth temperature film;
(7), by deposit the print of high growth temperature film immerse diluted acid, and ultrasonic processing, remove fast the hard mask of zinc paste and on the high growth temperature film, then with deionized water, clean up, finally with nitrogen, dry up, complete and prepare high growth temperature film pattern layer on substrate.
In the present invention, described substrate is applicable to photoetching technique and anti-500 ℃ of materials to 1000 ℃ of high temperature.
In the present invention, described high growth temperature membraneous material comprises ferroelectric material or the semiconductor materials such as ruthenic acid strontium, bismuth ferrite, barium strontium titanate, strontium titanates, barium titanate or lead zirconate titanate;
In the present invention, the impact of described source of oxygen ion etching reply substrate etching is less than 5 nanometers.
In the present invention, described deposition apparatus comprises: the deposition apparatus such as physical vapor deposition (PVD), chemical vapor deposition (CVD), pulsed laser deposition (PLD) or electron beam evaporation (EB).
In the present invention, described positive photoresist thickness and zinc paste mask plate Thickness Ratio at 3:1 between 10:1.
In the present invention, described zinc paste mask plate thickness and high growth temperature film thickness than 1:1 between 10:1.
Diluted acid of the present invention can be fast corrosion oxidation zinc but to high growth temperature thin film corrosive acidic materials slowly, and such as watery hydrochloric acid, phosphoric acid,diluted etc., its volumetric concentration is not generally higher than 20%.
The invention has the advantages that and break through the limitation that conventional lithography glue can not be used in hot environment, after utilizing cheap zinc paste mask plate conversion photoetching offset plate figure, can prepare various new materials and make new construction etc. at hot environment (below 1000 ℃).
The accompanying drawing explanation
Fig. 1 utilizes conventional lithography glue to shift square figure, 1 micron of positive photoresist thickness.
Fig. 2 200 Nano zinc oxide films are grown on the positive photoresist figure.
Fig. 3 removes the hard mask plate of zinc paste after positive photoresist.
600 ℃ of growth 100 nanometer ruthenic acid strontium films on the hard mask plate of Fig. 4 zinc paste.
The square figure of Fig. 5 ruthenic acid strontium film.
Number in the figure: 100 is substrate, and 101 is the positive photoresist figure, and 200 is 200 Nano zinc oxide film layers, and 201 is hollow out figure in zinc oxide film, and 300 is 100 nanometer ruthenic acid strontium thin layers, and 301 is the square figure of 100 nanometer ruthenic acid strontium film.
Embodiment
Hereinafter in conjunction with being shown in reference example, more specifically describe the present invention, the invention provides preferred embodiment, but should not be considered to only limit to embodiment set forth herein.
Fig. 1 displaying utilizes conventional lithographic techniques, makes the square figure 101 of 1 micron thick on substrate by lithography with positive photoresist.Litho pattern should be followed principle: the positive photoresist figure is consistent with final graphics.Remove slightly the photoresist of non-photoresist covering place on substrate by source of oxygen afterwards in the ion etching machine residual.
On the sample shown in Fig. 1, use at room temperature deposit of physical vapor deposition (PVD) method 200 Nano zinc oxide film layers 200, as shown in Figure 2.Afterwards, print immerses in acetone soln, puts into ultrasonic machine ultrasonic 5 minutes, positive photoresist figure 101 and on Nano zinc oxide film layer 200 remove, last print immerses in ethanol solution and cleans 10 seconds, and dries up with nitrogen.Now the print structure as shown in Figure 3, hollow out figure 201 mean positive photoresist figure 101 and on 200 hollow out figures after removing, bottom is substrate.In order to ensure positive photoresist figure 101 photoresists, remove totally, it is residual that print is removed slightly on substrate hollow out figure 201 place's photoresists by source of oxygen subsequently in the ion etching machine.Finally, print (1000 ℃ of oxygen atmosphere, temperature) short annealing 10 minutes in quick anneal oven, thus make zinc-oxide film by the amorphous crystal structure that is changed to.Now the zinc oxide films rete with figure is high temperature resistant hard mask plate.
Utilize the high temperature resistant hard mask plate of zinc paste, in pulsed laser deposition system (PLD), the ruthenic acid strontium film of deposit one deck 100 nanometers at 600 ℃ of temperature, as Fig. 4.The square figure 301 of nanometer ruthenic acid strontium film means that 100 nanometer ruthenic acid strontium films directly are deposited on substrate, afterwards, print immerses in the phosphoric acid,diluted of volume ratio 15%, put into ultrasonic machine ultrasonic 2 minutes, guarantee zinc oxide films rete 200 and on ruthenic acid strontium thin layer 300 all remove, and spend immediately ionized water and clean up print, use nitrogen to dry up, be successfully prepared sample, as shown in Figure 5.
Claims (6)
1. a high temperature resistant hard mask plate preparation method is characterized in that concrete steps are as follows:
, on substrate, prepare by photoetching technique the positive photoresist figure that thickness is 200 nanometers to 5 micron;
(2), residual with the photoresist of the positive photoresist graphics field of photolithographic exposure and the removal of developing on source of oxygen removal substrate in the ion etching machine;
, in deposition apparatus, on the substrate with the positive photoresist figure, under room temperature, deposition thickness is the zinc oxide films retes of 50 nanometers to 500 nanometers, obtains print;
, by above-mentioned print immerse positive photoresist on acetone soln ultrasonic removal substrate and on the zinc oxide films rete, then with absolute ethyl alcohol, clean up, and dry up with nitrogen;
(5), residual with the photoresist of non-oxide zinc covering place on source of oxygen removal print substrate in the ion etching machine, subsequently print in quick anneal oven, under oxygen atmosphere, 500 ℃ to 1000 ℃ high temperature rapid thermal annealings 5 minutes to 30 minutes, make zinc-oxide film by the amorphous crystal structure that is changed to;
, in deposition apparatus, on the structure obtained in step (5), in 200 ℃ to 1000 ℃ temperature environments, deposition thickness is the high growth temperature films of 10 nanometers to 500 nanometers; The material of described high growth temperature film is ruthenic acid strontium, bismuth ferrite, barium strontium titanate, strontium titanates, barium titanate or lead zirconate-titanate ferroelectric material, or semiconductor material;
(7), by deposit the print of high growth temperature film immerse diluted acid, and ultrasonic processing, remove fast the hard mask of zinc paste and on the high growth temperature film, then with deionized water, clean up, finally with nitrogen, dry up, complete and prepare high growth temperature film pattern layer on substrate.
2. high temperature resistant hard mask plate preparation method according to claim 1, is characterized in that, described substrate is applicable to photoetching technique and anti-500 ℃ of materials to 1000 ℃ of high temperature.
3. high temperature resistant hard mask plate preparation method according to claim 1, is characterized in that, described deposition apparatus is physical vapor deposition equipment, chemical vapor deposition device, pulsed laser deposition equipment or electron beam evaporation deposition apparatus.
4. high temperature resistant hard mask plate preparation method according to claim 1, is characterized in that, described positive photoresist thickness and zinc paste mask plate Thickness Ratio at 3:1 between 10:1.
5. high temperature resistant hard mask plate preparation method according to claim 1, is characterized in that, described zinc paste mask plate thickness and high growth temperature film thickness than 1:1 between 10:1.
6. high temperature resistant hard mask plate preparation method according to claim 1, is characterized in that, described diluted acid is watery hydrochloric acid or phosphoric acid,diluted, and its volumetric concentration is not higher than 20%.
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| CN201210161659.6A CN102650821B (en) | 2012-05-23 | 2012-05-23 | Method for preparing high-temperature resistant hard photomask |
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| CN201210161659.6A CN102650821B (en) | 2012-05-23 | 2012-05-23 | Method for preparing high-temperature resistant hard photomask |
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| CN102650821B true CN102650821B (en) | 2014-01-08 |
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| JP2006047539A (en) * | 2004-08-03 | 2006-02-16 | Toppan Printing Co Ltd | Photomask and its manufacturing method |
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| JP2008015098A (en) * | 2006-07-04 | 2008-01-24 | Japan Science & Technology Agency | Photomask, exposure device and method |
| CN101419400A (en) * | 2007-10-24 | 2009-04-29 | 中国科学院微电子研究所 | Method for dry etching through metal chromium masking film |
| WO2011027972A2 (en) * | 2009-09-02 | 2011-03-10 | 위아코퍼레이션 주식회사 | Laser-reflective mask and method for manufacturing same |
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Patent Citations (6)
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|---|---|---|---|---|
| US6617215B1 (en) * | 2002-03-27 | 2003-09-09 | Advanced Micro Devices, Inc. | Memory wordline hard mask |
| JP2006047539A (en) * | 2004-08-03 | 2006-02-16 | Toppan Printing Co Ltd | Photomask and its manufacturing method |
| CN1740909A (en) * | 2005-09-26 | 2006-03-01 | 广辉电子股份有限公司 | Optical mask and producing method thereof |
| JP2008015098A (en) * | 2006-07-04 | 2008-01-24 | Japan Science & Technology Agency | Photomask, exposure device and method |
| CN101419400A (en) * | 2007-10-24 | 2009-04-29 | 中国科学院微电子研究所 | Method for dry etching through metal chromium masking film |
| WO2011027972A2 (en) * | 2009-09-02 | 2011-03-10 | 위아코퍼레이션 주식회사 | Laser-reflective mask and method for manufacturing same |
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| Fabrication of PEDOT PSSZnMgO Schottky- type ultraviolet sensors on glass substrates with solution- based mist deposition technique and hard- mask patterning;Takumi Ikenoue et al.;《Phys.Status Solidi C 8》;2011(第2期);613-615 * |
| GaN- based light- emitting diodes with pillar structures around the mesa region;P.H.Chen et al.;《IEEE journal of quantum electronics》;201007;第46卷(第7期);1066-1071 * |
| GaN-based LEDs with mesh ITO p-contact and nanopillars;Wei-Chih Lai et al.;《IEEE photonics technology letters》;20090915;第21卷(第18期);1293-1295 * |
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