CN100461483C - Method for reducing heating electrode area of phase-change memory - Google Patents
Method for reducing heating electrode area of phase-change memory Download PDFInfo
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- CN100461483C CN100461483C CNB2006100281072A CN200610028107A CN100461483C CN 100461483 C CN100461483 C CN 100461483C CN B2006100281072 A CNB2006100281072 A CN B2006100281072A CN 200610028107 A CN200610028107 A CN 200610028107A CN 100461483 C CN100461483 C CN 100461483C
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Abstract
A method for decreasing area of heating electrode on phase transition storage includes applying nano-processing technique to prepare hole with diameter of 200-500nm on SiO2 substrate, applying CVD technique to pack W and TiN heating material in said hole then carrying out chemical-mechanical polishing to form column type of heating electrode, growing quantum dot on said heating electrode and oxidizing quantum dot to be insulation material to decrease effective area of column type of heating electrode.
Description
Technical field
The present invention relates to a kind of method that reduces heating electrode area of phase-change memory, specifically a kind of quantum dot that has insulating property (properties) by preparation on the column heating electrode of large-size, thereby reduce the actual effective area of heating electrode, reduce the contact area of heating electrode and phase-change material, improve heating current density.Thereby just avoided the difficulty of direct preparation nanometer heating electrode (100nm is following), reduced manufacturing cost, the more important thing is the power consumption that has reduced phase transition storage.The preparation technology and the electrical characterization field that belong to nano material in the microelectronics.
Background technology
In present novel memory technology, phase transition storage (chalcogenide based RAM based on sulphur based semiconductor material, C-RAM) it is low to have a cost, speed is fast, the storage density height, make simple and with the current good outstanding advantage of CMOS (complementary metal-oxide-semiconductor) ic process compatibility, be subjected to worldwide extensive concern.In addition, C-RAM has performances such as anti-irradiation (ability of resistant to total dose is greater than 1Mrad (Si)), high-low temperature resistant (-55-125 ℃), against violent vibration are moving, anti-electronic jamming, in national defence and aerospace field important application prospects is arranged.From 2003, international semiconductor TIA thinks that always phase transition storage most possibly replaces present SRAM (static RAM), current main products such as DRAM (dynamic random access memory) and FLASH memory (flash memory) and become the semiconductor storage unit of future generation of following memory main product, USA space council delivers statement recently: think: the C-RAM technology is the breakthrough of the highly reliable computer chip material of high safety, the research of this memory technology provides unprecedented guarantee for war with computer chip, and this technology may cause the change of the revolution of computer.
Main in the world electronics and semiconductor company all is being devoted to the development of C-RAM at present.There are Ovonyx, Intel, Samsung, IBM, Bayer, ST Micron, AMD, Panasonic, Sony, Philips, British Areospace, Hitachi and Macronix etc. in main research unit.In May, 2005, American I BM, German Infineon science and technology, Taiwan Macronix International (Macronix International) are announced joint study exploitation phase transition storage, send 20～25 technical staff to participate in this research specially.3 companies provide the technology of being good at separately to study respectively, specifically, exactly with the relevant material that IBM is had and the basic research ability of physical characteristic, the research of the various internal memory products that Infineon has, exploitation and volume production technical capability, and the non-voltile memory technical capability of Macronix International is integrated in this research.
Present situation at present C-RAM fast development, want to realize as early as possible its practicability, industrialization, reach the target of " faster, littler, colder ", the C-RAM device size must further dwindle, in the device phase-change material undergo phase transition the zone size and heating electrode size further dwindle, reach deep-submicron so that nanometer scale, undergo phase transition required current/voltage, reduce the power consumption of phase-changing memory unit thereby reduce the sulphur based material.
As prepare at present more than the method for phase transition storage is to utilize the method for various etchings to prepare small holes on dielectric substrate, fills phase-change material or electrode material then.For example utilize electron beam exposure and reactive ion etching technology on dielectric layer, to prepare the nanometer aperture, in aperture, fill heating electrode material (as W, Pt etc.) with the method for magnetron sputtering W then, form nano-electrode through polishing again.But when the diameter of aperture when 200nm is following, fill relatively difficulty of W or other heating material therein, materials such as W often just are deposited in the aperture, are difficult to enter in the hole, have a lot of cavities in the hole, cause loose contact even open circuit.In addition, obtain the following hole of 100nm diameter, itself is also relatively more difficult, and hole is more little, makes trouble more, and manufacturing cost is also high more.The present invention is exactly at the difficulty that how to overcome the micro-nano process technology and reduces manufacturing cost, realizes reducing the nanometer heating electrode of phase-change storage real area and a kind of simple, the practical new that proposes.
Summary of the invention
The invention provides a kind of preparation method who reduces heating electrode area of phase-change memory.At the difficulty of filling metal material (W, Pt) in the present nanoscale hole with further reduce heating electrode area and reduce the target of power consumption, a kind of method that reduces heating electrode area of proposition.At first, SiO is arranged in length by the micro-nano process technology
2Or prepare the hole of large-size (200-500nm) on the substrate of other medium, then utilize CVD or PVD technology in this hole, to fill METAL HEATING PROCESS material (W etc. have the metal material of certain resistivity), carry out chemico-mechanical polishing (CMP) after filling up, thereby form columnar electrode.Innovative point of the present invention is: the method for utilizing the quantum dot of the insulation that covers one deck dispersion on larger-diameter column heating electrode, reduce the purpose that heating electrode area reduces device power consumption thereby reach, both avoid the difficulty of the filling electrode material of small size nano aperture, can reduce the cost of making the small size electrode again.The present invention simultaneously is applicable to not only how solution reduces the problem of nanometer heating electrode of phase-change storage, is equally applicable to the particularly preparation of the required small size nano-electrode of nanometer electronic device of other electronic device, has great practical value.
Main technique step of the present invention is as follows:
(a) utilize high vacuum magnetically controlled sputter method deposit one deck hearth electrode on Si substrate or other substrate, the thick SiO of in-situ sputtering growth 200nm-500nm on hearth electrode
2, SiN
x, Al
2O
3, ZrO
2A kind of Deng in the dielectric layer;
(b) utilize electron beam exposure, reactive ion etching technology or current sub-micron CMOS prepared nano aperture on above-mentioned dielectric layer, the diameter of hole is at 200nm-500nm, and hole passes dielectric layer, and the hole bottom links to each other with hearth electrode;
(c) utilizing magnetron sputtering or PVD technology to fill resistivity in the aperture that step (b) is made is 10
-4-10
-2The material of ohmcm;
(d) filling up resistivity in the hole is 10
-4-10
-2After the material of ohmcm, adopt chemico-mechanical polishing (CMP) technology, the material that aperture is outer is removed, and obtains columnar electrode;
(e) on the above-mentioned substrate that has a columnar electrode, utilize the process of CVD or PVD to prepare the quantum dot of a certain size and density; For example utilize SiH
4In plasma enhanced CVD (PECVD) system, prepare semiconductor Si quantum dot with the mist of Ar, then at O
2Be oxidized to SiO under the atmosphere
2Quantum dot, the size 5～10nm of quantum dot, density 10
10-10
11/ cm
2Because the insulator that disperses is to the covering of column heating electrode, the actual effective area of column heating electrode reduces greatly;
(f) or on the above-mentioned substrate that has a columnar electrode utilize the method for electron beam evaporation to prepare the metal quantum point, as W, Al quantum dot etc., size is 3～5nm, and density is 10
10/ cm
2Then the metal quantum point oxidation that disperses is formed the insulator quantum dot that disperses.Because the insulator quantum dot that disperses is to the covering of column heating electrode, the actual effective area of column heating electrode reduces greatly;
(g) on the substrate of above-mentioned columnar electrode, prepare phase-change material, heat-insulating material and upper electrode material, by peeling off or the method for etching forms the phase transformation memory device unit array;
(h) above-mentioned phase transformation memory device unit with column heating electrode is connected in the electrical measurement system, carry out the writing of phase transformation memory device unit, wiping, read operation, study its storage characteristics and fatigue properties, study its current-voltage (I-V) characteristic, resistance-stream (R-I) characteristic, electric current-time (I-t) characteristic etc., phase change current is less than 0.1mA, and resistance differs one more than the magnitude before and after the phase transformation.
Described backing material is unrestricted, can be the Si sheet of using always, and semi-conducting materials such as GaAs also can be dielectric material or metal materials such as quartz glass, ceramic substrate.
Described hearth electrode is unrestricted, can be conductor material commonly used such as aluminium, copper, and its thickness is 200-400nm.
Described dielectric material is SiO commonly used
2, SiN
x, Al
2O
3, ZrO
2Deng material;
Hole on the described dielectric layer can use electron beam exposure and reactive ion etching method or current sub-micron CMOS process means to obtain.
The material of described heating electrode is that W etc. has certain resistivity (10
-4-10
-2Ohmcm) material, even can on electrodes such as W, then deposit heating material such as TiN, TiW, the TiAlN etc. of the high resistivity of the several nanometer thickness of one deck again, thus improve heats, reduce operating current.
Described quantum dot can be that (as Si quantum dot, Ge quantum dot etc., oxidation forms the SiO of insulation to all semiconductor-quantum-points that can form insulator after oxidation then
2, GeO
2Quantum dot etc.);
Described quantum dot also can be that (as Al quantum dot, Zr quantum dot etc., oxidation forms the Al of insulation to all metal quantum points that can form insulator after oxidation then
2O
3, Zr
2O
3Quantum dot etc.).
Described quantum dot can directly prepare the quantum dot of insulating material (as SiO on columnar electrode
2, ZrO
2, GeO
2Or Al
2O
3Deng);
Described stripping means is to have substrate surface coating one deck photoresist of column heating electrode earlier, then by exposing the columnar nanometer electrode zone after the cloudy reticle exposure, there is photoresist in other place, with acetone the photoresist beyond the columnar electrode zone is together removed the last only phase-change material of remaining electrode zone after having grown phase-change material together with the phase-change material on the photoresist.On the phase-change material of the electrode zone after peeling off, cover layer of insulation material again, draw top electrode at last, form phase-change memory device unit construction or its array.
The method of described etching is to prepare phase-change material, heat-insulating material and upper electrode material on the substrate of columnar electrode in succession having; by whirl coating, sunlight cut blocks for printing the exposure method; thereby the columnar electrode zone is protected with photoresist; utilize reactive ion etching or other lithographic method to remove columnar electrode upper electrode material, heat-insulating material and phase-change material in addition then, form phase transformation memory device unit.
In sum, the invention provides a kind of preparation method of simple, practical small size nanometer heating electrode of phase-change storage, the present invention is equally applicable to other device that need use nano-electrode.
Description of drawings
Cross-sectional view behind somatomedin material, hearth electrode and the heat-insulating material successively on Fig. 1 substrate.
The cross-sectional view of Fig. 2 after forming hole on the heat-insulating material.
Fig. 3 fills the cross-sectional view behind the heating electrode material in hole shown in Figure 2.
Fig. 4 fills up the structural representation of preparation insulation quantum dot behind the heating electrode material in hole.
The structural representation of Fig. 5 behind deposit one deck phase-change material on the structure of Fig. 4.
Fig. 6 peel off or the etching phase-change material after form the cross-sectional view of phase change material unit.
The structural representation of Fig. 7 deposit layer of insulation material again on the structure of Fig. 6.
The phase transformation memory device unit that Fig. 8 obtains after forming contact hole on the heat-insulating material and preparing top electrode.
Among the figure 1, dielectric layer; 2, hearth electrode; 3, heat insulation layer a; 4, column heating electrode; 5, insulation quantum dot; 6, phase-change material; 7, heat insulation layer b; 8, top electrode.
Embodiment
Below by specific embodiment, further illustrate substantive distinguishing features of the present invention and obvious improvement, but the present invention only is confined to described embodiment by no means.
Embodiment 1:
(1) the thick SiO of heat growth 100nm on the Si substrate
2Or utilize PECVD (plasma enhanced chemical vapor deposition) to prepare the thick SiN of 100nm
xDeielectric-coating is then at SiO
2Or SiN
xOn utilize the method for magnetron sputtering or evaporation to prepare the thick Al film of one deck 80nm as hearth electrode, utilize PECVD or sputtering method on hearth electrode A1, to prepare the thick SiO of 300nm-500nm at last
2(Fig. 1)
(2) at SiO
2On utilize electron beam exposure and reactive ion etching technology to prepare hole, hole bottom links to each other with hearth electrode, hole diameter is in the 200nm-500nm scope; (Fig. 2)
(3) utilize CVD or sputtering technology in hole, to fill the W material, fill up until hole.Utilize chemical Mechanical Polishing Technique (CMP) to throw then and remove the W material of hole with exterior domain; (Fig. 3)
(4) utilize PECVD or magnetron sputtering or ultra vacuum electron beam evaporation method preparation Si quantum dot on the above-mentioned substrate that has a columnar electrode; The used source of the gas of PECVD is SiH
4With the mist of Ar, the used target of magnetron sputtering is the Si target, and the used evaporation source of ultra vacuum electron beam evaporation is the Si particle; The base vacuum degree is 10
-3Below the Pa; The size of Si quantum dot is 5～10nm, and density is 10
10-10
11/ cm
2Method by oxidation forms SiO with the oxidation of Si quantum dot then
2Quantum dot; (Fig. 4)
(5) magnetron sputtering prepares phase-change material GeSbTe, and thickness 40-100nm, base vacuum are 3 * 10
-6Torr, the sputter vacuum is 0.08Pa, power 100W; (Fig. 5)
(6) utilize and to peel off or lithographic technique is prepared phase-change material GeSbTe unit, phase change material unit is at the 5-20 micron; (Fig. 6)
(7) utilize magnetron sputtering or ultra vacuum electron beam evaporation method around above-mentioned phase change material unit, to cover layer of insulation material SiO
2, SiNx etc.; (Fig. 7)
(8) by peeling off or etching formation contact hole, evaporation etching Al film forms top electrode; (Fig. 8)
(9) this phase transformation memory device unit is connected between two probes of electrical measurement system, just can carries out research of writing, wiping operation and memory property, fatigue properties of phase transformation memory device unit etc.
Embodiment 2:
Utilize magnetron sputtering or vacuum electron beam method of evaporating to prepare the Al quantum dot the 4th step of embodiment 1, the used target of magnetron sputtering is the Al target instead, and the used source of vacuum electronic beam evaporation is the Al particle, and the base vacuum degree is 10
-3Below the Pa, Al quantum dot size is 3～5nm, and density is 10
10/ cm
2Then the oxidation of Al quantum dot is formed Al
2O
3Quantum dot, other can obtain result similar to Example 1 with the step of embodiment 1.
Embodiment 3:
Utilize magnetron sputtering or vacuum electron beam method of evaporating to prepare Al the 4th step of embodiment 1 instead
2O
3, ZrO
2Or the quantum dot of other insulating material, the used target of magnetron sputtering is Al
2O
3, ZrO
2Deng target, the used source of vacuum electronic beam evaporation is Al
2O
3, ZrO
2Deng particle, the base vacuum degree is 10
-3Below the Pa, Al
2O
3, ZrO
2The quantum dot size is 10～15nm, and density is 10
10/ cm
2Other can obtain result similar to Example 1 with the step of embodiment 1.
Embodiment 4:
Change the substrate of embodiment 1 into pottery, quartz or other insulative material substrate, sputter thereon prepares the thick SiO of 100nm
2Or utilizing PECVD to prepare the thick SiNx deielectric-coating of 100nm, other can obtain result similar to Example 1 with embodiment one.
Embodiment 5:
After embodiment 1 the 3rd step filling W material, and then on the W material, prepare several nanometer thickness of one deck again and have more heating material such as TiW, the TiN etc. of high resistivity, other step is with embodiment one.Can obtain better heating effect like this, reduce the operating current of device.
Claims (9)
1. a method that reduces heating electrode area of phase-change memory at first by the micro-nano process technology, has SiO in length
2Or the hole of preparation 200-500nm size on the substrate of other medium, then utilize CVD or PVD technology in this hole, to fill the METAL HEATING PROCESS material, carry out chemico-mechanical polishing after filling up, form the column heating electrode, it is characterized in that: on formed column heating electrode, cover the quantum dot of the insulation of one deck dispersion, reduce the purpose that heating electrode area reduces device power consumption thereby reach.
2. by the described a kind of method that reduces heating electrode area of phase-change memory of claim 1, it is characterized in that concrete steps are:
(a) utilize high vacuum magnetically controlled sputter method deposit one deck hearth electrode on Si substrate or other substrate, the thick SiO of in-situ sputtering growth 200nm-500nm on hearth electrode
2, SiN
x, Al
2O
3Or ZrO
2A kind of in the dielectric layer;
(b) utilize electron beam exposure and reactive ion etching technology or sub-micron CMOS prepared nano aperture on the dielectric layer that step (a) obtains, the diameter of hole is at 200nm-500nm, and hole passes dielectric layer, and the hole bottom links to each other with hearth electrode;
(c) utilizing magnetron sputtering or PVD method to fill resistivity in the aperture that step (b) is made is 10
-4-10
-2The material of ohmcm;
(d) filling up resistivity in the hole is 10
-4-10
-2After the material of ohmcm, adopt cmp method, the material that aperture is outer is removed, and obtains the column heating electrode;
3. by the described a kind of method that reduces heating electrode area of phase-change memory of claim 2, it is characterized in that utilizing on the prepared substrate that has a column heating electrode of step (d) method of CVD or PVD to prepare the quantum dot of a certain size and density; Described quantum dot is to utilize SiH
4In the plasma enhanced CVD system, prepare semiconductor Si quantum dot with the mist of Ar, then at O
2Be oxidized to SiO under the atmosphere
2Quantum dot, the size 5～10nm of quantum dot, density 10
10-10
11/ cm
2
4. by the described a kind of method that reduces heating electrode area of phase-change memory of claim 2, it is characterized in that utilizing the method for electron beam evaporation to prepare W or Al metal quantum point on the prepared substrate that has a column heating electrode of step (d), size is 3～5nm, and density is 10
10/ cm
2Then the metal quantum point oxidation that disperses is formed the insulator quantum dot that disperses.
5. by claim 1 or 2 described a kind of methods that reduce heating electrode area of phase-change memory, it is characterized in that described backing material is Si sheet, GaAs, quartz glass or ceramic substrate.
6. by the described a kind of method that reduces heating electrode area of phase-change memory of claim 2, it is characterized in that described hearth electrode is Al or Cu, thickness is 200-400nm.
7. by the described a kind of method that reduces heating electrode area of phase-change memory of claim 2, it is characterized in that described resistivity is 10
-4-10
-2The material of ohmcm is metal W or the heating material that deposits the high resistivity of several nanometer thickness of one deck on the column heating electrode, and described high resistance heating material is TiN, TiW or TiAlN.
8. by claim 1 or 2 described a kind of methods that reduce heating electrode area of phase-change memory, the step that it is characterized in that forming the insulation quantum dot of dispersion comprises: form Ge quantum dot or Zr quantum dot on column heating electrode substrate.
9. by the described a kind of method that reduces heating electrode area of phase-change memory of claim 8, it is characterized in that described Ge quantum dot or Zr quantum dot form insulator and be respectively GeO after oxidation
2Or ZrO
2
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| CN101572290B (en) * | 2009-06-02 | 2010-09-08 | 中国科学院上海微系统与信息技术研究所 | Method for preparing columnar nanometer heating electrode |
| CN102386323B (en) * | 2010-09-03 | 2013-12-11 | 中芯国际集成电路制造(上海)有限公司 | Phase change memory element and manufacturing method thereof |
| CN102637823B (en) * | 2012-05-16 | 2014-03-26 | 中国科学院上海微系统与信息技术研究所 | Limited electrode structure for low-power-consumption phase change memory and preparation method thereof |
| CN104300081B (en) * | 2013-07-15 | 2017-05-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Heating electrode of phase change memory and manufacturing method thereof |
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| US6841793B2 (en) * | 2002-08-23 | 2005-01-11 | Samsung Electronics Co., Ltd. | Phase-changeable devices having an insulating buffer layer and methods of fabricating the same |
| CN1714405A (en) * | 2002-12-13 | 2005-12-28 | 奥沃尼克斯股份有限公司 | Forming phase change memories |
| CN1616572A (en) * | 2004-09-24 | 2005-05-18 | 中国科学院上海微系统与信息技术研究所 | Nano polishing liquid for sulfuric compound phase changing material chemical mechanical polishing and its use |
| US7023008B1 (en) * | 2004-09-30 | 2006-04-04 | Infineon Technologies Ag | Resistive memory element |
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