CN103094476A - Undamaged etching method of phase change alloy materials - Google Patents
Undamaged etching method of phase change alloy materials Download PDFInfo
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- CN103094476A CN103094476A CN2013100185056A CN201310018505A CN103094476A CN 103094476 A CN103094476 A CN 103094476A CN 2013100185056 A CN2013100185056 A CN 2013100185056A CN 201310018505 A CN201310018505 A CN 201310018505A CN 103094476 A CN103094476 A CN 103094476A
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Abstract
The invention provides an undamaged etching method of phase change alloy materials. The method comprises a first step of providing a semiconductor substrate, a second step of forming a phase change alloy material layer on the semiconductor substrate, a third step of forming an etching barrier layer on the upper surface of the phase change alloy material layer, a fourth step of imaging the etching barrier layer to enable the surface of the phase change alloy material layer in preinstall part to be exposed, a fifth step of immersing the surface of the exposed phase change alloy material layer into etching gas with hydrogen bromide and helium and a sixth step of exciting the etching gas into plasmas to etch the exposed phase change alloy material layer to the semiconductor substrate. The undamaged etching method of the phase change alloy materials has the advantages that due to the fact that the etching gas with the hydrogen bromide is adopted, sideetching in the process of etching can be reduced. Due to the fact that the helium severs as inert gas, the occurrence that the property of the material surface is changed due to the introduction of oxygen or nitrogen can be avoided, and therefore a phase change alloy material pattern which is clean, smooth and steep is achieved, and the side wall of the phase change alloy material pattern is not damaged.
Description
Technical field
The present invention relates to integrated circuit and make the field, relate in particular 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 spare, and the conductivity or the optical characteristics difference that show when utilizing the phase-change alloy material mutually to transform between crystalline state and amorphous state are come the data storage.Phase transition storage have read at a high speed, high erasable number of times, the advantage such as non-volatile, device size is little, low in energy consumption and manufacturing process is simple, can replace multiple traditional memory, 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 chalcogenide compound normally in phase transition storage, as germanium-antimony-tellurium, silicon-antimony-alloys such as tellurium.Industry is extensively by etching technics, the phase-change alloy material to be carried out graphical definition at present, and is incorporated in the making of phase transition storage.Because the phase-change alloy material is not common materials in conventional semiconductor processing, therefore, a lot of new problems have been faced when carrying out graphical definition by etching technics.
In phase-change alloy material plasma etching technics, the fluoride of chlorine or carbon is usually as main etching gas.Due to the chemical reaction that occurs between halogen in etching process and phase-change alloy material, phase-change alloy material sidewall can produce etching injury.Introducing nitrogen or oxygen can cause the material surface composition to drift about equally in etching process.Along with constantly dwindling of process node, the live width of phase-change alloy material is also more and more less, and impact will be more and more serious on device performance by the sidewall damage.
Figure 1 shows that the fluoride that adopts chlorine or carbon is as main etching gas, carry out the resulting phase-change alloy material profile of etching schematic diagram, comprise Semiconductor substrate 110, be arranged in successively phase-change alloy material figure 112 and the etching barrier layer 122 on this Semiconductor substrate 110 surfaces.
Fig. 2 a-Fig. 2 b is depicted as the cross section transmission electron microscope photo of phase-change alloy material after the fluoride etching that adopts chlorine and carbon.Can see clearly from figure, due to the sideetching effect that produces when the fluoride that adopts chlorine or carbon is main etching gas, the sidewall surfaces of phase-change alloy material is coarse, the phenomenon of undercutting and element loss occurs.These be in actual process do not wish the result that obtains.
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, is used for solving the problem of sidewall damage in prior art phase-change alloy material etching.Can avoid sideetching and element loss to the phase-change alloy material, thereby obtain to have the phase-change alloy material figure of the smooth steep sidewall of cleaning.
In order to address the above problem, the invention provides a kind of harmless lithographic method of phase-change alloy material, comprise the steps: to provide semi-conductive substrate;
Form the phase-change alloy material layer on this Semiconductor substrate;
Upper surface at described phase-change alloy material layer forms etching barrier layer;
Graphical described etching barrier layer is so that come out in the surface of the phase-change alloy material layer of predetermined fraction;
The surface of the phase-change alloy material layer that comes out is immersed in the etching gas that contains hydrogen bromide and helium;
Described etching gas is excited into phase-change alloy material layer that plasma comes out with etching 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 was excited into plasma, chamber pressure was 1～100mT; Plasma 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 hydrogen bromide as the main chemical reactions gas of etching, and adopt helium to carry out physical bombardment, can form cleaning, smooth, the steep and phase-change alloy material figure that damages without sidewall.
Description of drawings
Accompanying drawing 1 is depicted as the existing fluoride that adopts chlorine or carbon as etchant gas, the schematic cross-section that the phase-change alloy material that carries out obtaining after etching consists of.
Accompanying drawing 2a-Fig. 2 b is depicted as the existing fluoride that adopts chlorine and carbon as etchant gas, the section transmission electron microscope photo that the phase-change alloy material that carries out obtaining after etching consists of.
Accompanying drawing 3 is depicted as the implementation step block diagram of the method embodiment of etching phase transformation alloy material provided by the invention.
Accompanying drawing 4 is depicted as provides phase-change alloy material alloys layer, and described phase-change alloy material layer is arranged in semiconductor substrate surface.
Accompanying drawing 5 is depicted as the surface coverage etching barrier layer at the phase-change alloy material layer.
Accompanying drawing 6 is depicted as the described etching barrier layer of patterning, so that come out in the surface of the phase-change alloy material layer of predetermined portions.
Accompanying drawing 7 is depicted as the process chart of the method embodiment of etching phase transformation alloy material provided by the invention.
Accompanying drawing 8 is depicted as the schematic cross-section of the phase-change alloy material formation that obtains after the method embodiment of etching phase transformation alloy material provided by the invention.
Accompanying drawing 9 is depicted as the section electromicroscopic photograph that obtains after the concrete implementing process of method of etching phase transformation alloy material provided by the invention.
The element numbers explanation
Embodiment
Below by specific instantiation explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification.The present invention can also be implemented or be used by other different embodiment, and the every details in this specification also can be based on different viewpoints and application, carries out various modifications or change under spirit of the present invention not deviating from.
See also shown in accompanying drawing.Need to prove, the diagram that provides in the present embodiment only illustrates basic conception of the present invention in a schematic way, satisfy only show in graphic with the present invention in relevant assembly but not component count, shape and size drafting when implementing according to reality, during its actual enforcement, kenel, quantity and the ratio of each assembly can be a kind of random change, and its assembly layout kenel also may be more complicated.
Elaborate below in conjunction with the method embodiment of accompanying drawing to etching phase transformation alloy material provided by the invention.Accompanying drawing 3 is depicted as the implementation step schematic diagram of this embodiment, and concrete steps are as follows:
Step S110 provides Semiconductor substrate, forms the phase-change alloy material layer on this Semiconductor substrate;
Step S120 forms etching barrier layer on the surface of described phase-change alloy material;
Step S130, graphical described etching barrier layer is so that come out in the surface of the phase-change alloy material layer of predetermined portions; Step S140 is immersed in the etching gas of the mixed atmosphere formation that contains hydrogen bromide and helium the surface of the phase-change alloy material layer that exposes;
Step S150 is excited into plasma with etching gas, with etching phase transformation alloy material layer to the described Semiconductor substrate.
Accompanying drawing 4 is depicted as the process chart of this embodiment to accompanying drawing 7.Wherein, Figure 4 shows that step S110 concrete structure schematic diagram afterwards.Semi-conductive substrate 210 is provided, forms phase-change alloy material layer 220 on this Semiconductor substrate 210.Described Semiconductor substrate 210 can be silicon substrate or other compound semiconductor substrate.Soi structure for example.
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.
See also shown in accompanying drawing 5, refer step S120 is at the surface coverage etching barrier layer 230 of described phase-change alloy material layer 220.The material of described etching barrier layer 230 is photoresist preferably.Photoresist is easily to carry out graphically as the advantage of etching barrier layer.The material of described etching barrier layer 230 can be also metal hard mask, the hard mask of dielectric medium or other layered mask etc.
Such as: commonly in this areas such as silica, silicon nitride or titanium nitride be used for carrying out the material that etching stops.
See also shown in accompanying drawing 6, refer step S130, graphical described etching barrier layer 230 namely forms some grooves 231, so that the phase-change alloy material layer 220 of default figure comes out on this etching barrier layer.Described patterned etching barrier layer can adopt the method for photoetching common in this area and lithographic method or electron beam exposure to form, and does not repeat them here.After this step enforcement is complete, forms etching in the surface of described phase-change alloy material layer 220 and stop figure.
See also shown in accompanying drawing 7, refer step S140, the using plasma lithographic method continues etching in the etching gas that the mixed atmosphere that the surface of the phase-change alloy material layer that exposes is immersed in contain hydrogen bromide and helium forms.
Refer step S150, the etching gas that mixed atmosphere is formed is excited into plasma, and the phase-change alloy material layer that exposes with etching is until on 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, adopt hydrogen bromide in the present embodiment, the process conditions that adopt and parameter can be: the source power of reative cell 1～100mT(1mT=0.133Pa), plasma exciatiaon is 300～700 watts, bias voltage is 250～400 volts, the 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; participate in the etching of phase-change alloy material take hydrogen bromide as main corrosive gas; than milder, itself can produce the metal halide protective side wall at the material sidewall with the fluoride etching phase of chlorine or carbon, thereby forms steep smooth and without the sidewall of etching injury.Experiment shows adopts hydrogen bromide as sidewall the best of the formula acquisition of main etching gas.
Because the etching gas that contains hydrogen bromide is reactive material, in the etching gas that passes in step S140, the described composition gas that contains hydrogen bromide and helium can obtain best technological effect in the situation that ratio matches (HBr and He volume ratio are roughly 1:3).Experiment shows, the etching gas that contains hydrogen bromide is easier to obtain to clean, smooth, steep sidewall.Accompanying drawing 9 comprises substrate 310, phase-change alloy material figure 320 and etching barrier layer 330 for adopting the transmission electron microscope schematic diagram of the phase-change alloy material layer figure with steep smooth sidewall that obtains after above-mentioned embodiment.Compare with accompanying drawing 2 and can significantly find out the phase-change alloy material figure that adopts this specific implementation method can obtain steep sidewall, the damage that in etching process, oppose side wall causes has simultaneously also obtained reduction.
In sum, the present invention has effectively overcome various shortcoming of the prior art and the tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not is used for restriction the present invention.Any person skilled in the art scholar all can under spirit of the present invention and category, modify or change above-described embodiment.Therefore, have in technical field under such as and know that usually the knowledgeable modifies or changes not breaking away from all equivalences of completing under disclosed spirit and technological thought, must be contained by claim of the present invention.
Claims (5)
1. the harmless lithographic method of a phase-change alloy material, is characterized in that, comprises the steps:
Semi-conductive substrate is provided;
Form the phase-change alloy material layer on this Semiconductor substrate;
Upper surface at described phase-change alloy material layer forms etching barrier layer;
Graphical described etching barrier layer is so that come out in the surface of the phase-change alloy material layer of predetermined fraction;
The surface of the phase-change alloy material layer that comes out is immersed in the etching gas that contains hydrogen bromide and helium;
Described etching gas is excited into phase-change alloy material layer that plasma comes out with etching 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 was excited into plasma, chamber pressure was 1～100mT; Plasma source power is 300～700 watts; Bias voltage is 250～400 volts.
5. the harmless lithographic method of phase-change alloy material according to claim 4, it is characterized in that, when making the surface of the phase-change alloy material layer that comes out be immersed in the etching gas that contains hydrogen bromide and helium, the hydrogen bromide flow is 100～250sccm, and helium gas flow is 100～500sccm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111696863A (en) * | 2019-03-15 | 2020-09-22 | 北京北方华创微电子装备有限公司 | Silicon medium material etching method |
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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***与信息技术研究所 | Dry etching method of phase change material |
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| US20080026586A1 (en) * | 2006-07-31 | 2008-01-31 | Hong Cho | Phase change memory cell and method and system for forming the same |
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080026586A1 (en) * | 2006-07-31 | 2008-01-31 | Hong Cho | Phase change memory cell and method and system for forming the same |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN111696863A (en) * | 2019-03-15 | 2020-09-22 | 北京北方华创微电子装备有限公司 | Silicon medium material etching method |
| 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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