CN101958397B - Manufacture method of resistor storage - Google Patents
Manufacture method of resistor storage Download PDFInfo
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- CN101958397B CN101958397B CN2009100549785A CN200910054978A CN101958397B CN 101958397 B CN101958397 B CN 101958397B CN 2009100549785 A CN2009100549785 A CN 2009100549785A CN 200910054978 A CN200910054978 A CN 200910054978A CN 101958397 B CN101958397 B CN 101958397B
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Abstract
The invention relates to a manufacture method of a resistor storage, which comprises the steps of: providing a bottom electrode, wherein the bottom electrode is sequentially provided with a storage medium layer and an oxidization medium layer, the storage medium layer has the characteristic of a binary resistor; reducing one side of the oxidization medium layer far away from the storage medium layer to form a reduced metal layer; forming a top electrode on the reduced metal layer; and annealing the oxidization medium layer and the reduced metal layer to ensure that at least part of reduced metal layer is used for reducing the oxidization medium layer. Compared with the prior art, the reduced metal layer can be better coupled with an upper electrode, and the protection of the storage medium layer below the reduced metal layer is provided. In addition, according to the invention, the oxygen content in the storage medium layer can be controlled and regulated, and the resistor conversion property of a storage medium is improved.
Description
Technical field
The present invention relates to technical field of manufacturing semiconductors, particularly relate to a kind of manufacturing approach of Memister.
Background technology
Current, development cost is low, speed is fast, storage density is high, manufacturing is simple and receive worldwide extensive concern with the compatible good novel memory technology of current CMOS (CMOS) semiconductor integrated circuit technique.Resistive random access memory (RRAM based on metal oxide with resistance switch characteristic; Abbreviate Memister as) memory techniques be the emphasis of at present how tame device manufacturer exploitation because this technology can provide more high density, the more low-cost and Nonvolatile memory of low power consumption more.The memory cell of RRAM resistance value after applying pulse voltage can produce great changes, and this resistance value still can be kept down behind deenergization.In addition, RRAM has performances such as anti-irradiation, high-low temperature resistant, against violent vibration are moving, anti-electronic jamming.
RRAM comprises a plurality of memory cell; Fig. 1 has provided a kind of structure of the memory cell of RRAM; Described memory cell comprises the hearth electrode (BE, Bottom Electrode) 120 in the dielectric layer 110 that is formed on the Semiconductor substrate 100, is formed on the storage medium 130 of the resistance-variable on the hearth electrode 120; And be formed on the top electrode (TE, Top Electrode) 150 on the storage medium 130.Hearth electrode 120 is an electric conducting material, for example is tungsten (W), metallic copper (Cu) etc.; Storage medium 130 comprises the dielectric film with binary resistance characteristic 131 that the said hearth electrode 120 of oxidation forms, and it can be changed between high-impedance state and low resistance state under outer field action, and storage medium 130 also comprises connection medium 130.The information of more structure and manufacturing approaches about RRAM can application reference number is the Chinese invention patent application of 200410038012.X.
The oxygen content of storage medium is the key factor that influences resistance conversion (conversion between high-impedance state and the low resistance state) performance, and therefore, how the oxygen content in the regulating and controlling storage medium also is the problem that needs solve.
In addition, prior art is easy to generate the situation of hyperoxidation when forming the storage medium of resistance-variable, also promptly formed the immutable oxide layer of one deck resistance on the storage medium top layer, thereby influenced the memory property of RRAM.
Summary of the invention
The technical problem that the present invention solves is: the oxygen content in the regulating and controlling storage medium how, improve the resistance conversion performance of storage medium.
For addressing the above problem, the present invention provides a kind of manufacturing approach of Memister, comprises step: hearth electrode is provided, is provided with storage medium layer and oxide isolation layer on the said hearth electrode successively, said storage medium layer has the binary resistance characteristic; Reduce said oxide isolation layer away from a side of storage medium layer, form the reducing metal layer; On the layer of said reducing metal, form top electrode; Said oxide isolation layer and said reducing metal layer are carried out annealing in process, make at least the partial reduction metal level reduce said oxide isolation layer.
Alternatively, the method for formation storage medium layer and oxide isolation layer specifically comprises step on hearth electrode: it is the hearth electrode of reacting metal that the top is provided, and said reacting metal is the metal that has the binary resistance characteristic after the oxidation; The said reacting metal layer of oxidation forms storage medium layer that is connected with said hearth electrode and the oxide isolation layer that is connected with said storage medium layer.
Alternatively, said reacting metal and said hearth electrode are different metals, and said reacting metal is formed on the said hearth electrode through deposition or electric plating method.
Alternatively, said reacting metal and said hearth electrode are metals of the same race.
Alternatively, the said reacting metal layer of said oxidation, the step that forms storage medium layer that is connected with said hearth electrode and the oxide isolation layer that is connected with said storage medium layer is specially: the top layer of the said reacting metal layer of partial oxidation forms the oxide isolation layer; Said reacting metal layer and said oxide isolation layer are carried out annealing in process, make the bottom reaction of said reacting metal layer of part and oxide isolation layer, generate storage medium layer.
Alternatively, said reacting metal is selected from alloy one or any several kinds in copper, tungsten, tantalum, titanium, nickel and the cobalt.
Alternatively, the thickness of said reacting metal layer is 2 to 20nm.
Alternatively, specifically comprise step: with first oxide of method deposition reaction metal on hearth electrode of chemical vapour deposition (CVD) or physical vapour deposition (PVD), formation storage medium layer in the method that forms storage medium layer and oxide isolation layer on the hearth electrode; With second oxide of method deposition reaction metal on storage medium layer of chemical vapour deposition (CVD) or physical vapour deposition (PVD), form the oxide isolation layer, the oxygen content of said second oxide is higher than first oxide.
Alternatively, the oxygen content of said oxide isolation layer is higher than said storage medium layer.
Alternatively, said partial reduction metal level reduces behind the said oxide isolation layer, and the partial reduction metal level of participating in reaction is oxidized to identical with the oxygen content of said storage medium layer, and said oxide isolation layer is reduced into identical with the oxygen content of said storage medium layer.
Alternatively, Restore All metal level and said oxide isolation layer carry out redox reaction, and after reaction was accomplished, the Restore All metal level all formed the oxide identical with said storage medium layer with said oxide isolation layer.
Alternatively, the temperature of said annealing in process is 100 to 400 ℃, and the time is 5 to 30min.
Compared with prior art, the present invention forms one deck reducing metal layer, can be coupled with top electrode preferably, and the protection to the storage medium layer under it is provided.
In addition, the present invention forms storage medium layer that is connected with said hearth electrode and the oxide isolation layer that is connected with said storage medium layer earlier.Restore the side of said oxide isolation layer, form the reducing metal layer away from storage medium layer.At last said oxide isolation layer and said reducing metal layer are carried out annealing in process, make at least the partial reduction metal level reduce said oxide isolation layer.Can effectively reduce with the control store dielectric layer in oxygen content, thereby can improve the resistance conversion performance of storage medium.
Description of drawings
Fig. 1 is the structural representation of prior art Memister;
Fig. 2 is the flow chart of the manufacturing approach of one embodiment of the invention Memister;
Fig. 3 to Fig. 7 is a sketch map of making Memister according to flow process shown in Figure 2.
Embodiment
Embodiment of the present invention is through in the process of making Memister, forms storage medium layer that is connected with said hearth electrode and the oxide isolation layer that is connected with said storage medium layer earlier.Restore the side of said oxide isolation layer, form the reducing metal layer away from storage medium layer.At last said oxide isolation layer and said reducing metal layer are carried out annealing in process, make at least the partial reduction metal level reduce said oxide isolation layer.Can effectively reduce with the control store dielectric layer in oxygen content, thereby can improve the resistance conversion performance of storage medium.
According to above-mentioned thought, a kind of manufacturing approach of memory cell of Memister is provided in embodiment, as shown in Figure 2, comprise step:
Step S201, it is the hearth electrode of reacting metal that the top is provided;
Step S202, the said reacting metal layer of oxidation forms storage medium layer and oxide isolation layer;
Step S203 forms the reducing metal layer;
Step S204 forms top electrode on the layer of said reducing metal;
Step S205 carries out annealing in process to said oxide isolation layer and said reducing metal layer.
Be elaborated below in conjunction with accompanying drawing.
As shown in Figure 3, execution in step S201 at first, it is the hearth electrode 220 of reacting metal 230 that the top is provided.Execution in step S201 specifically can comprise: Semiconductor substrate 200 is provided and is positioned at the dielectric layer 210 on the Semiconductor substrate 200; In dielectric layer 210, form hearth electrode 220; On hearth electrode, form reacting metal 230.
Said Semiconductor substrate 200 can be doped silicon or semi-conducting materials such as silicon-on-insulator and SiGe.Described dielectric layer 210 is located immediately on the Semiconductor substrate 200; In multilevel integration, described dielectric layer 210 can also be the one deck in the multilayer insulation dielectric material, i.e. an interlayer dielectric layer on the Semiconductor substrate.The material of said dielectric layer 210 can be silicon dioxide or fluorine silex glass insulating material such as (FSG), adopts chemical vapor deposition (CVD) technology to be formed on the Semiconductor substrate 200 usually.For example transistor etc. of semiconductor device can be formed with in said Semiconductor substrate 200 and the dielectric layer 210, other input or output circuit or line (indicating among the figure) can also be formed with.
The formation technology of hearth electrode 220 can have the preparation method who fills the hole ability for chemical vapour deposition (CVD), ald (ALD), magnetron sputtering, physical deposition, electron beam evaporation, thermal evaporation etc.Preferably; Adopt chemical vapor deposition method; Concrete formation method is described below: in said dielectric layer 210, form opening (not indicating among the figure); Said opening and the source electrode of Semiconductor substrate semiconductor device or being electrically connected of drain electrode perhaps are electrically connected with the circuit that inputs or outputs that other need be connected; Adopt chemical vapor deposition method on opening inwall and interlayer dielectric layer 210, to form barrier layer (not indicating among the figure), the material on said barrier layer for example is a titanium nitride (TiN); On said barrier layer, adopt the chemical vapour deposition technique deposits conductive material then; Adopt CMP process to remove barrier layer and electric conducting material on the dielectric layer 210 at last, form hearth electrode 220, expose dielectric layer 210.
The electric conducting material that forms said hearth electrode 220 is unrestricted; Can use tungsten (W), platinum (Pt), aluminium (Al), copper (Cu), nickel (Ni), cobalt (Co), molybdenum (Mo), gold (Au), ruthenium (Ru), iridium (Ir), silver (Ag), palladium (Pd), titanium (Ti), tantalum (Ta) etc. to be suitable as the metal material of Memister hearth electrode; Preferably, select metal Cu or W for use.
The material of said reacting metal layer 230 should be the dielectric film with binary resistance characteristic, and the character of semi-conducting material is generally arranged.The metal material that forms reacting metal layer 230 can be selected the wherein a kind of of Cu, W, Ni, Co, Mo, Ta and Ti for use or comprise in the aforementioned metal any one or a few alloy.Resistance has switching characteristic after these metal material oxidations.The thickness range of the reacting metal layer 230 that forms can be 2 nanometer to 20 nanometers.
When hearth electrode 220 adopts the different metallic material with reacting metal layer 230; Can adopt the deposition process or the electric plating method of chemical vapour deposition (CVD) or physical vapour deposition (PVD); Directly deposit metallic material on hearth electrode 220 forms the reacting metal layer 230 that is connected with hearth electrode 220.
Execution in step S202 is as shown in Figure 4 then, and oxidation reaction metal level 230 forms storage medium layer 231 and oxide isolation layer 232.The concrete grammar of oxidation reaction metal level 230 is preferably selects plasma treatment method for use, and the metal material of direct oxidation reacting metal layer 230 forms storage medium layer 231 and oxide isolation layer 232.Those skilled in the art understand, if the oxygen plasma body burden and the processing time of control plasma treatment, just can disposable formation storage medium layer 231 and oxide isolation layer 232.
The another kind of method that forms storage medium layer 231 and oxide isolation layer 232 is: the top layer of partial oxidation reaction metal level 230 forms the higher oxide isolation layer 232 of oxygen content; Reacting metal layer 230 and oxide isolation layer 232 are carried out annealing in process, the partial reaction metal level 230 and the bottom of oxide isolation layer 232 are reacted, generate the lower storage medium layer 231 of oxygen content.
When hearth electrode 220 adopted identical metal material with reacting metal layer 230, the another kind of method that forms storage medium layer 231 and oxide isolation layer 232 was: oxidation reaction metal level 230 forms the higher oxide isolation layer 232 of oxygen content; Oxide isolation layer 232 and hearth electrode 220 are carried out annealing in process, make the bottom reaction of the top layer and the oxide isolation layer 232 of hearth electrode 220, generate the lower storage medium layer 231 of oxygen content.
In the above-described embodiments, storage medium layer 231 and oxide isolation layer 232 are that method through oxidation reaction metal level 230 realizes.But; The present invention is not limited to this; The method that forms storage medium layer 231 and oxide isolation layer 232 can also be: the lower valency oxide with method deposition reaction metal on hearth electrode 220 of chemical vapour deposition (CVD) or physical vapour deposition (PVD) forms storage medium layer 231; With the high valence state oxide of method deposition reaction metal on storage medium layer 231 of chemical vapour deposition (CVD) or physical vapour deposition (PVD), form oxide isolation layer 232 then.The oxygen content of the high valence state oxide here is higher than the oxygen content of lower valency oxide.
Execution in step S203 is as shown in Figure 5 then, forms reducing metal layer 240.The method that forms reducing metal layer 240 can be to utilize plasma H
2O, CH
4, C
2H
4, C
2H
6Perhaps CH
3OH etc. contain H gas, form the reproducibility plasma, form reducing metal layer 240 with the top layer of this reproducibility plasma deoxidization oxide isolation layer 232 then.The time of Cement Composite Treated by Plasma is 1 to 5 minute, and treatment temperature is 100 ℃ to 200 ℃.And the material of formed here reducing metal layer 240 actual be exactly the material of the reacting metal layer 230 that provides among the step S201.
Behind step S203, can form the reducing metal layer 240 of a layer thickness on the surface of remaining oxide isolation layer 232 greater than oxide isolation layer 232.Step S203 reduces among the present invention and control store dielectric layer 231 interior oxygen contents, thereby improves the committed step of the resistance conversion performance of storage medium layer 231.The control of article on plasma body processing time and treatment temperature is exactly to control of Oxygen Content in the storage medium layer 231 among the step S203.Because the thickness of reducing metal layer 240 greater than oxide isolation layer 232, therefore, in subsequent process, can reduce oxide isolation layer 232 by demand.
Execution in step S204 is as shown in Figure 6 then, on reducing metal layer 240, forms top electrode 250.Forming top electrode 250 can be earlier reducing metal layer 240 to be carried out wet-cleaned, avoids layer 240 surface in reducing metal to exist oxide residual.And then adopt for example chemical vapor deposition method or physical gas-phase deposition etc., form the top electrode 250 that covers reducing metal layer 240.The material of said top electrode can be metal A l, titanium nitride (TiN), tantalum nitride metal nitrides such as (TaN), and perhaps noble metal such as metal Pt and other are suitable as the electric conducting material of Memister top electrode.
Last execution in step S205 carries out annealing in process to oxide isolation layer 232 and reducing metal layer 240, makes the bottom of oxide isolation layer 232 and reducing metal layer 240 partly carry out redox reaction, generates the coating identical with the material of storage medium layer 231.Also be the bottom of oxide isolation layer 232 and reducing metal layer 240 carries out redox reaction in the process of annealing after; The bottom of oxide isolation layer 232 and reducing metal layer 240 and original storage medium layer merge; Form thicker storage medium layer 231 '; And reducing metal layer 240 becomes thinner, or even participates in reaction fully.
The temperature of above-mentioned annealing process is 100 ℃ to 400 ℃, and the time is 5 minutes to 30 minutes.In annealing process; Because reducing metal layer 240 is covered by top electrode 250 fully; Can't absorb oxygen (for example airborne oxygen) from the upper strata; Thereby can only be directly and the reaction of the oxide isolation layer 232 under it, thereby make the bottom of reducing metal layer 240 be oxidized to the part of storage medium layer 231 ' with binary resistance characteristic; Simultaneous oxidation dielectric layer 232 also has been reduced into the part of the storage medium layer 231 ' with binary resistance characteristic.Like this; Between hearth electrode 220 and the top electrode 250 except being the reducing metal layer 240 of conductor fully; Remaining metal oxide has all become the part of storage medium layer 231 ' and has had the binary resistance characteristic, therefore, and before memory cell is write data; Bring the step of the puncture oxide isolation layer 232 of negative effect with regard to having saved the reliability that can give RRAM, and then the operating time of having simplified memory cell.
And,, therefore reduced the oxygen content of storage medium layer 231 ' effectively because reducing metal layer 240 has absorbed the oxygen of the oxide isolation layer 232 under it; Simultaneously, through oxygen content, improved the resistance conversion performance of storage medium to the selection controllable adjustable storage medium layer 231 ' of the thickness of reducing metal layer 240 and annealing conditions.
Though the present invention discloses as above with preferred embodiment, the present invention is defined in this.Any those skilled in the art are not breaking away from the spirit and scope of the present invention, all can do various changes and modification, so protection scope of the present invention should be as the criterion with claim institute restricted portion.
Claims (12)
1. the manufacturing approach of a Memister is characterized in that, comprises step:
Hearth electrode is provided, is provided with storage medium layer and oxide isolation layer on the said hearth electrode successively, said storage medium layer has the binary resistance characteristic;
Contain H gas through ionization, form the reproducibility plasma, utilize the side of the said oxide isolation layer of said reproducibility plasma deoxidization, form the reducing metal layer away from storage medium layer;
On the layer of said reducing metal, form top electrode;
Said oxide isolation layer and said reducing metal layer are carried out annealing in process, make at least the partial reduction metal level reduce said oxide isolation layer.
2. the manufacturing approach of Memister as claimed in claim 1 is characterized in that, the method that on hearth electrode, forms storage medium layer and oxide isolation layer specifically comprises step:
It is the hearth electrode of reacting metal layer that the top is provided, and the reacting metal of said reacting metal layer is the metal that has the binary resistance characteristic after the oxidation;
The said reacting metal layer of oxidation forms storage medium layer that is connected with said hearth electrode and the oxide isolation layer that is connected with said storage medium layer.
3. the manufacturing approach of Memister as claimed in claim 2, it is characterized in that: said reacting metal and said hearth electrode are different metals, said reacting metal is formed on the said hearth electrode through deposition or electric plating method.
4. the manufacturing approach of Memister as claimed in claim 2, it is characterized in that: said reacting metal and said hearth electrode are metals of the same race.
5. the manufacturing approach of Memister as claimed in claim 2 is characterized in that, the said reacting metal layer of said oxidation, and the step that forms storage medium layer that is connected with said hearth electrode and the oxide isolation layer that is connected with said storage medium layer is specially:
The top layer of the said reacting metal layer of partial oxidation forms the oxide isolation layer;
Said reacting metal layer and said oxide isolation layer are carried out annealing in process, make the bottom reaction of said reacting metal layer of part and oxide isolation layer, generate storage medium layer.
6. the manufacturing approach of Memister as claimed in claim 2, it is characterized in that: said reacting metal is selected from alloy one or any several kinds in copper, tungsten, tantalum, titanium, nickel and the cobalt.
7. the manufacturing approach of Memister as claimed in claim 2 is characterized in that: the thickness of said reacting metal layer is 2 to 20nm.
8. the manufacturing approach of Memister as claimed in claim 1 is characterized in that: the method that on hearth electrode, forms storage medium layer and oxide isolation layer specifically comprises step:
With first oxide of method deposition reaction metal on hearth electrode of chemical vapour deposition (CVD) or physical vapour deposition (PVD), form storage medium layer;
With second oxide of method deposition reaction metal on storage medium layer of chemical vapour deposition (CVD) or physical vapour deposition (PVD), form the oxide isolation layer, the oxygen content of said second oxide is higher than first oxide.
9. like the manufacturing approach of claim 1 or 8 described Memisters, it is characterized in that: the oxygen content of said oxide isolation layer is higher than said storage medium layer.
10. the manufacturing approach of Memister as claimed in claim 1; It is characterized in that: said partial reduction metal level reduces behind the said oxide isolation layer; The partial reduction metal level of participating in reacting is oxidized to identical with the oxygen content of said storage medium layer, and said oxide isolation layer is reduced into identical with the oxygen content of said storage medium layer.
11. the manufacturing approach of Memister as claimed in claim 1; It is characterized in that: Restore All metal level and said oxide isolation layer carry out redox reaction; After reaction was accomplished, the Restore All metal level all formed the oxide identical with said storage medium layer with said oxide isolation layer.
12. the manufacturing approach of Memister as claimed in claim 1 is characterized in that: the temperature of said annealing in process is 100 to 400 ℃, and the time is 5 to 30min.
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| CN2009100549785A CN101958397B (en) | 2009-07-16 | 2009-07-16 | Manufacture method of resistor storage |
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| CN101958397B true CN101958397B (en) | 2012-08-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130149815A1 (en) * | 2011-09-16 | 2013-06-13 | Hideaki Murase | Nonvolatile memory element manufacturing method and nonvolatile memory element |
| CN103682090B (en) * | 2012-09-17 | 2016-12-21 | 复旦大学 | The manufacture method of resistor-type memory and resistor-type memory |
| CN106299107A (en) * | 2015-05-25 | 2017-01-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Resistance-variable storing device of low formation voltage and preparation method thereof |
| CN111640866A (en) * | 2020-07-16 | 2020-09-08 | 上海华力微电子有限公司 | Resistive random access memory and preparation method thereof |
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| CN101159309A (en) * | 2007-11-08 | 2008-04-09 | 复旦大学 | Method for implementing low power consumption resistance memory |
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| CN101159309A (en) * | 2007-11-08 | 2008-04-09 | 复旦大学 | Method for implementing low power consumption resistance memory |
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| JP特开2007-300100A 2007.11.15 |
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