CN103094476B - The harmless lithographic method of phase change alloy material - Google Patents
The harmless lithographic method of phase change alloy material Download PDFInfo
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- CN103094476B CN103094476B CN201310018505.6A CN201310018505A CN103094476B CN 103094476 B CN103094476 B CN 103094476B CN 201310018505 A CN201310018505 A CN 201310018505A CN 103094476 B CN103094476 B CN 103094476B
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Abstract
The invention provides a kind of harmless lithographic method of phase change alloy material, comprise the steps: to provide semi-conductive substrate; This Semiconductor substrate is formed phase change alloy material layer; Etching barrier layer is formed at the upper surface of described phase change alloy material layer; Graphical described etching barrier layer, comes out with the surface of the phase change alloy material layer making predetermined fraction; In the etching gas that the surface of the phase change alloy material layer come out is immersed in containing hydrogen bromide and helium; Described etching gas is excited into plasma to etch on the phase change alloy material layer that comes out to described Semiconductor substrate.The invention has the advantages that, have employed the etching gas of hydrogen bromide, the sideetching in etching process can be reduced, helium is as inert gas, can avoid introducing oxygen or nitrogen and the material surface performance change that causes, thus obtain clean, smooth, steep and without the phase change alloy material figure of sidewall damage.<!--1-->
Description
Technical field
The present invention relates to IC manufacturing field, particularly relate to a kind of harmless lithographic method of phase change alloy material.
Background technology
Phase transition storage is a kind of novel non-volatile data memory part, and the conductivity showed when utilizing phase change alloy material mutually to transform between crystalline and amorphous or optical characteristics difference are carried out data and stored.Phase transition storage has at a high speed reading, high erasable number of times, the advantage such as non-volatile, device size is little, low in energy consumption and manufacturing process is simple, multiple traditional memory can be replaced, and be widely used in the fields such as consumer electronics such as mobile communication, mobile data terminal, mobile multimedia.
Be applied to the phase change alloy material normally chalcogenide compound in phase transition storage, as germanium-antimony-tellurium, the alloys such as silicon-antimony-tellurium.Current industry is extensively, by etching technics, phase change alloy material is carried out figure Shape definition, and is incorporated in the making of phase transition storage.Due to the common materials that phase change alloy material is not in conventional semiconductor processing, therefore, much new problem is encountered by when carrying out figure Shape definition by etching technics.
In phase change alloy material plasma etching industrial, the fluoride of chlorine or carbon is usually used as main etching gas.Due to the chemical reaction occurred between halogen and phase change alloy material in etching process, phase change alloy material sidewall can produce etching injury.Nitrogen is introduced or oxygen can cause material surface composition to drift about equally in etching process.Along with constantly reducing of process node, the live width of phase change alloy material is also more and more less, and it will be more and more serious for being affected device performance by sidewall damage.
Figure 1 shows that and adopt the fluoride of chlorine or carbon as main etching gas, carry out etching obtained phase change alloy material generalized section, comprise Semiconductor substrate 110, be arranged in phase change alloy material figure 112 and the etching barrier layer 122 on this Semiconductor substrate 110 surface successively.
Fig. 2 a-Fig. 2 b is depicted as the Cross-section transmission electromicroscopic photograph of the rear phase change alloy material of fluoride etching adopting chlorine and carbon.Can see clearly from figure, due to the sideetching effect of fluoride for producing during main etching gas at employing chlorine or carbon, the sidewall surfaces of phase change alloy material is coarse, occurs the phenomenon of undercutting and element loss.These are the results not wishing in actual process to obtain.
Given this, be necessary to provide a kind of new method to overcome the problems referred to above in fact.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of harmless lithographic method of phase change alloy material, for solving the problem of sidewall damage in phase change alloy material etching in prior art.The sideetching to phase change alloy material and element loss can be avoided, thus obtain the phase change alloy material figure with clean smooth steep sidewall.
In order to solve the problem, the invention provides a kind of harmless lithographic method of phase change alloy material, comprising the steps: to provide semi-conductive substrate;
This Semiconductor substrate is formed phase change alloy material layer;
Etching barrier layer is formed at the upper surface of described phase change alloy material layer;
Graphical described etching barrier layer, comes out with the surface of the phase change alloy material layer making predetermined fraction;
In the etching gas that the surface of the phase change alloy material layer come out is immersed in containing hydrogen bromide and helium;
Described etching gas is excited into plasma to etch on the phase change alloy material layer that comes out to described Semiconductor substrate.
As optional technical scheme, described phase change alloy material comprises antimony tellurium compound or germanium tellurium compound.
As optional technical scheme, when described etching gas is excited into plasma, chamber pressure is 1 ~ 100mT; Source power is 300 ~ 700 watts; Bias voltage is 250 ~ 400 volts.
As optional technical scheme, the material of described etching barrier layer is photoresist, metal hard mask, the hard mask of dielectric medium or other layered mask etc.
The invention has the advantages that and choose the main chemical reactions gas of hydrogen bromide as etching, and adopt helium to carry out physical bombardment, can be formed clean, smooth, steep and without the phase change alloy material figure of sidewall damage.
Accompanying drawing explanation
Attachedly Figure 1 shows that the fluoride of existing employing chlorine or carbon is as etchant gas, the schematic cross-section that the phase change alloy material obtained after etching is formed.
Accompanying drawing 2a-Fig. 2 b is depicted as the fluoride of existing employing chlorine and carbon as etchant gas, the Cross section transmission electromicroscopic photograph that the phase change alloy material obtained after etching is formed.
The attached implementation step block diagram that Figure 3 shows that the method embodiment of etching phase change alloy material provided by the invention.
Attached Figure 4 shows that provides phase change alloy material alloy-layer, and described phase change alloy material layer is arranged in semiconductor substrate surface.
The attached surface coverage etching barrier layer that Figure 5 shows that at phase change alloy material layer.
Attachedly Figure 6 shows that etching barrier layer described in patterning, come out with the surface of the phase change alloy material layer making predetermined portions.
The attached process chart that Figure 7 shows that the method embodiment of etching phase change alloy material provided by the invention.
Attached Figure 8 shows that the method embodiment of etching phase change alloy material provided by the invention after the schematic cross-section that forms of the phase change alloy material that obtains.
Attached Figure 9 shows that the concrete implementing process of method of etching phase change alloy material provided by the invention after the section electromicroscopic photograph that obtains.
Element numbers explanation
Embodiment
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Refer to shown in accompanying drawing.It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
Elaborate below in conjunction with the method embodiment of accompanying drawing to etching phase change alloy material provided by the invention.The attached implementation step schematic diagram that Figure 3 shows that this embodiment, concrete steps are as follows:
Step S110, provides Semiconductor substrate, and this Semiconductor substrate is formed phase change alloy material layer;
Step S120, forms etching barrier layer on the surface of described phase change alloy material;
Step S130, graphical described etching barrier layer, comes out with the surface of the phase change alloy material layer making predetermined portions; Step S140, in the surface of the phase change alloy material layer exposed is immersed in etching gas that the mixed atmosphere containing hydrogen bromide and helium formed;
Step S150, is excited into plasma by etching gas, to etch on phase transformation alloy material layer to described Semiconductor substrate.
Accompanying drawing 4 is to the attached process chart that Figure 7 shows that this embodiment.Wherein, Figure 4 shows that step S110 after concrete structure schematic diagram.Semi-conductive substrate 210 is provided, this Semiconductor substrate 210 forms phase change alloy material layer 220.Described Semiconductor substrate 210 can be silicon substrate or other compound semiconductor substrate.Such as soi structure.
The material of described phase change alloy material layer 220 can be germanium-antimony-tellurium, silicon-antimony-tellurium, titanium-antimony-tellurium, aluminium-antimony-tellurium or other antimony-tellurium compound and germanium-tellurium compound etc.
Refer to shown in accompanying drawing 5, refer step S120, at the surface coverage etching barrier layer 230 of described phase change alloy material layer 220.The material preferably photoresist of described etching barrier layer 230.Photoresist is easily to carry out graphically as the advantage of etching barrier layer.The material of described etching barrier layer 230 also can be metal hard mask, the hard mask of dielectric medium or other layered mask etc.
Such as: the material for carrying out etch stopper common in this areas such as silica, silicon nitride or titanium nitride.
Refer to shown in accompanying drawing 6, refer step S130, graphical described etching barrier layer 230, namely forms some grooves 231 on this etching barrier layer, comes out to make the phase change alloy material layer 220 of preset pattern.Described patterned etching barrier layer can adopt the method for photoetching common in this area and lithographic method or electron beam exposure to be formed, and does not repeat them here.After this step is implemented, form etch stopper figure in the surface of described phase change alloy material layer 220.
Refer to shown in accompanying drawing 7, refer step S140, using plasma lithographic method, continue to etch in the surface of the phase change alloy material layer exposed is immersed in etching gas that the mixed atmosphere containing hydrogen bromide and helium formed.
Refer step S150, is excited into plasma by the etching gas that mixed atmosphere is formed, to etch the phase change alloy material layer that exposes until in Semiconductor substrate 210.Accompanying drawing 8 is the structural representations after etching.
Above-mentioned method for etching plasma is the common method in this area, hydrogen bromide is adopted in the present embodiment, the process conditions adopted and parameter can be: reative cell 1 ~ 100mT(1mT=0.133Pa), the source power of plasma exciatiaon is 300 ~ 700 watts, bias voltage is 250 ~ 400 volts, hydrogen bromide flow is 100 ~ 250sccm(1sccm=1 ml/min), helium gas flow is 100 ~ 500sccm.In the present embodiment, the volume ratio of hydrogen bromide and helium is roughly 1:3.
In plasma etch process; corrosive gas based on hydrogen bromide participates in the etching of phase change alloy material; with the fluoride etching phase of chlorine or carbon than milder, itself can produce metal halide protective side wall at material side wall, thus is formed steep smooth and without the sidewall of etching injury.Experiment shows the sidewall the best adopting hydrogen bromide to obtain as the formula of main etching gas.
Because the etching gas containing hydrogen bromide is reactive material, in the etching gas passed in step S140, the described composition gas containing hydrogen bromide and helium, when ratio matches (HBr and He volume ratio is roughly 1:3), can obtain the technological effect of the best.Experiment shows, the etching gas containing hydrogen bromide is easier to obtain clean, smooth, steep sidewall.Accompanying drawing 9 is the transmission electron microscope schematic diagram with the phase change alloy material layer pattern of steep smooth sidewall obtained after adopting above-mentioned embodiment, comprises substrate 310, phase change alloy material figure 320 and etching barrier layer 330.Significantly can find out the phase change alloy material figure adopting this specific implementation method can obtain steep sidewall compared with accompanying drawing 2, the damage that in etching process, oppose side wall causes simultaneously have also been obtained reduction.
In sum, the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (4)
1. a harmless lithographic method for phase change alloy material, is characterized in that, comprise the steps:
Semi-conductive substrate is provided;
This Semiconductor substrate is formed phase change alloy material layer;
Etching barrier layer is formed at the upper surface of described phase change alloy material layer;
Graphical described etching barrier layer, comes out with the surface of the phase change alloy material layer making predetermined fraction;
In the etching gas that the surface of the phase change alloy material layer come out is immersed in containing hydrogen bromide and helium; Hydrogen bromide flow is 100 ~ 250sccm, and helium gas flow is 100 ~ 500sccm;
Described etching gas is excited into plasma to etch on the phase change alloy material layer that comes out to described Semiconductor substrate.
2. the harmless lithographic method of phase change alloy material according to claim 1, is characterized in that, described phase change alloy material is antimony tellurium compound or germanium tellurium compound.
3. the harmless lithographic method of phase change alloy material according to claim 1, is characterized in that, the material of described etching barrier layer is the hard mask of photoresist, metal hard mask or dielectric medium.
4. the harmless lithographic method of phase change alloy material according to claim 1, is characterized in that, when described etching gas is excited into plasma, chamber pressure is 1 ~ 100mT; Source power is 300 ~ 700 watts; Bias voltage is 250 ~ 400 volts.
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| CN111244272A (en) * | 2020-01-19 | 2020-06-05 | 中国科学院上海微系统与信息技术研究所 | Dry etching method of phase change material |
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| CN105197876B (en) * | 2014-06-20 | 2017-04-05 | 中芯国际集成电路制造(上海)有限公司 | A kind of semiconductor devices and preparation method, electronic installation |
| CN111696863B (en) * | 2019-03-15 | 2024-04-12 | 北京北方华创微电子装备有限公司 | Silicon dielectric material etching method |
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| CN101768743A (en) * | 2008-12-30 | 2010-07-07 | 中芯国际集成电路制造(上海)有限公司 | Method for etching germanium antimony tellurium alloy materials |
| CN102447061A (en) * | 2011-12-12 | 2012-05-09 | 华中科技大学 | Preparation method of high-speed low-power-consumption phase change memory |
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| KR100838527B1 (en) * | 2006-07-31 | 2008-06-17 | 삼성전자주식회사 | Method for forming a phase change memory device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101768743A (en) * | 2008-12-30 | 2010-07-07 | 中芯国际集成电路制造(上海)有限公司 | Method for etching germanium antimony tellurium alloy materials |
| CN102447061A (en) * | 2011-12-12 | 2012-05-09 | 华中科技大学 | Preparation method of high-speed low-power-consumption phase change memory |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111244272A (en) * | 2020-01-19 | 2020-06-05 | 中国科学院上海微系统与信息技术研究所 | Dry etching method of phase change material |
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