CN1933207A - Phase transformation memory storing unit and producing method thereof - Google Patents
Phase transformation memory storing unit and producing method thereof Download PDFInfo
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Abstract
This invention relates to a phase-transformation storage unit and its preparation method charactering in covering a lower electrode layer on the substrate, covering a heat insulation material layer with holes on the lower electrode layer, and the holes contain a hollow column heating electrode material structure conducting to the lower electrode, a heat insulation material layer covers the column heating electrode and contains holes matched to the heating electrode and an inverse phase-transformation material layer covered by a heat insulation material layer with holes is contained in the electrode holes and the holes of the insulation material layer, and the upper electrode material is filled in the holes of the heat insulation layer conducting to the phase-transformation material, which limits the phase-transformation material in the holes in the hollow post and the insulation material to keep the phase-transformation material to be transformed first at the environment high temperature and high pressure when electric pulse operates a storage unit.
Description
Technical field
The present invention relates to a kind of phase-change memory storage unit structure and preparation method thereof, specifically a kind of heating electrode of preparing open column shape by the micro-nano process technology, and in open tubular column, fill phase-change material, utilization variation induced transformation material phase transformation of temperature and pressure in the open tubular column under the electric pulse effect, thus realize low pressure, low-power consumption, the high-speed functions of phase-change memory cell.The invention belongs to the microelectronics technical field.
Background technology
Phase transition storage (C-RAM, Chalcogenide-Random Access Memory) technology is based on Ovshinsky at late 1960s (Phys.Rev.Lett., 21,1450～1453,1968) beginning of the seventies (Appl.Phys.Lett., 18,254～257,1971) phase-change thin film of Ti Chuing can be applied to that the conception of phase change memory medium sets up.The characteristics of C-RAM memory critical material phase-change alloy are can make material between amorphous state and polycrystalline attitude reversible transition take place when giving its electric pulse.Present high resistant when being in amorphous state, present low-resistance during the polycrystalline attitude, amplitude of variation can reach several magnitude.But because the restriction of technology of preparing and technology, phase-change material can only just undergo phase transition than under the highfield, and this has just limited the process of its practicability development.Along with the development of nanometer technology of preparing and technology, effective phase change region size of phase-change material can narrow down to nanometer scale in the device, and material undergoes phase transition that required voltage reduces greatly, power consumption reduces, and great variety has also taken place the performance of material simultaneously.
C-RAM memory owing to have reads at a high speed, high erasable number of times, non-volatile, component size is little, low in energy consumption, advantages such as cost is low, can multistagely store, anti-strong motion and radioresistance, thought flash memories that most possible replacement is present by international semiconductor TIA and become following memory main product and become the device of commercial product at first.
Major companies such as Ovonyx, Intel, Samsung, STMicroelectronics, Hitachi, IBM, Toshiba, Philips and Panasonic are only arranged in the world in the research of carrying out the C-RAM memory, carrying out at present that technology is improved and the R﹠D work of manufacturability aspect.At the beginning of 2006, Samsung company adopts the technology of 0.12 μ m to prepare the C-RAM memory test print of 256M, but the operating current of device is also bigger, and power consumption is higher, and the stability of device is still waiting further raising.The C-RAM memory realizes that one of business-like key is reducing of storage operation electric current, at present the major measure that adopts be reduce between heating electrode material and the phase-change material contact area, increase heating electrode material and phase-change material resistance, improve device architecture design etc.Korea S Samsung has adopted the cellular construction of a kind of being called " On-axis confined ", phase-change material and heating electrode material all are limited in the hole of nanoscale, the zone that can reduce to undergo phase transition like this, improve the heat efficiency, make decrystallized (RESET) electric current of device cell reduce to 0.4mA[Symposium on VLSI Technology Digest ofTechnical Papers, 2005,6B-1,96].In order to reduce the contact area of heating electrode and phase-change material, Korea S Samsung has adopted a kind of ring-type heating electrode structure again, can adjust contact area by the wall thickness of control ring-type heating electrode like this, can reduce operating current greatly, but their ring-type heating electrode structure not a hollow, but filled certain insulating material, such structure can't make phase-change material be limited to [Jpn.J.Appl.Phys. in the heating electrode, 2006,45,3233].Recently, reports such as Kolobov, the phase transition process of phase-change material is not only relevant with temperature effect, and also have direct relation with pressure, they discover, apply certain pressure after, even if phase-change material is not heated, also can induce it to undergo phase transition [Phys.Rev.Lett., 2006,97:035701].
Just be based on above several principle, the present invention proposes and a kind ofly phase-change material is incorporated in the heating electrode of open column shape by heat treated way, because microcapillary effect, gas in the nanotube of one end sealing is difficult to discharge, just be sealed in the heating electrode of open column shape by phase-change material, the phase-change memory storage unit structure of Huo Deing has just possessed following advantage like this: 1) annular heating electrode reduces the contact area of electrode and phase-change material greatly; 2) the phase-change material volume that is introduced in the open column shape heating electrode is very little, and also very little with the contact area of heating electrode, is easy to undergo phase transition; 3) under the effect of electric pulse, because temperature raises, the volume expansion in the open column shape heating electrode is compressed phase-change material, makes phase-change material be in high temperature, the hyperbaric environment, is highly susceptible to undergoing phase transition; 4) after the phase-change material in the column heating electrode undergoes phase transition, can further induce other phase-change material to undergo phase transition, thereby reduce the required power consumption of phase transformation greatly.It more than is exactly design starting point of the present invention.
Summary of the invention
The objective of the invention is to seek structure of a kind of phase-change memory storage unit of realizing low pressure, low-power consumption, high speed storing and preparation method thereof.Concrete preparation process is as follows:
1) on substrate, prepare lower electrode layer (as shown in Figure 1), adopt thin film preparation process, its method be in sputtering method, evaporation, plasma ion assisted deposition method, chemical vapour deposition technique and the atomic layer deposition method any one.Substrate wherein is silicon substrate, glass, GaAs, the SiO on silicon chip, the insulating barrier
2, in plastics or the crystalline material any one; Electrode material is the monometallic material, for a kind of in the monometallic material among W, Pt, Au, Ti, Al, Ag, Cu or the Ni, or its alloy material that is combined into.
2) on bottom electrode, cover insulation material layer (as shown in Figure 2), the method for employing be in sputtering method, evaporation, atomic layer deposition method, plasma ion assisted deposition method, chemical vapour deposition technique, metallo-organic decomposition process and the laser assistant depositing method any one; Insulating material wherein is the mixture of a kind of or at least two kinds of formations in oxide, nitride, carbide, the sulfide.
3) by the micro-nano process technology, in insulation material layer, prepare hole, the diameter of hole is 10-500nm (as shown in Figure 3), the micro-nano process technology of employing be in conventional photoetching technique, focused-ion-beam lithography technology, atomic force microscope process technology, electron beam lithography method, extreme ultraviolet photolithographic method, nano impression method or the semiconductor standard processes any.
4) in hole, utilize thin film preparation processes such as chemical vapor deposition (CVD), ald (ALD) or physical vapor deposition (PVD) to fill heating electrode material, make it to communicate with bottom electrode, carry out chemico-mechanical polishing (CMP) then, remove unnecessary heating electrode material on the insulation material layer, form the open column shape heating electrode, the internal diameter size of open tubular column is controlled by adjusting CVD, ALD or PVD process time, is generally 5-490nm; Heating electrode material is a kind of among W, TiN, TiON, GeWN, GeTiN, TiW, GeN or the SiGe (as shown in Figure 4).
5) on the column heating electrode, cover insulation material layer (as shown in Figure 5), the method for employing be in sputtering method, evaporation, atomic layer deposition method, plasma ion assisted deposition method, chemical vapour deposition technique, metallo-organic decomposition process and the laser assistant depositing method any one; Insulating material wherein is the mixture of a kind of or at least two kinds of formations in oxide, nitride, carbide, the sulfide; The thickness of insulation material layer is 10-300nm.
6) in insulation material layer, prepare hole (as shown in Figure 6) with column heating electrode alignment, the diameter of hole is 10-2000nm, the micro-nano process technology of employing be in conventional photoetching technique, focused-ion-beam lithography technology, atomic force microscope process technology, electron beam lithography method, extreme ultraviolet photolithographic method, nano impression method or the semiconductor standard processes any.
7) deposition reversible transition material (as shown in Figure 7) in the hole on the column heating electrode, adopt thin film preparation process, preparation method be in sputtering method, evaporation, Metalorganic Chemical Vapor Deposition, chemical vapour deposition technique and the atomic layer deposition method any one; Described chalcogenide compound is for containing a kind of compound of the 6th major element at least; The thickness of phase-change material layers is 10-500nm.
8) under atmosphere protection, carry out annealing in process, the partial phase change material entered in the open tubular column of heating electrode, annealing temperature be higher than phase-change material glass transformation temperature, be lower than in the scope of fusion temperature; Used protective gas is Ar, N
2, O
2, among He or the Ne any (as shown in Figure 8).
9) on phase-change material layers, prepare heat-insulating material (as shown in Figure 9), the method for employing be in sputtering method, evaporation, atomic layer deposition method, plasma ion assisted deposition method, chemical vapour deposition technique, metallo-organic decomposition process and the laser assistant depositing method any one; Insulating material wherein is the mixture of a kind of or at least two kinds of formations in oxide, nitride, carbide, the sulfide; The thickness of insulation material layer is 50-500nm.
10) by the micro-nano process technology, in insulation material layer, prepare hole (as shown in figure 10), the micro-nano process technology of employing be in conventional photoetching technique, focused-ion-beam lithography technology, atomic force microscope process technology, electron beam lithography method, extreme ultraviolet photolithographic method, nano impression method or the semiconductor standard processes any.
11) in hole, fill electrode material, make it to communicate (as shown in figure 11) with phase-change material, used method be in sputtering method, evaporation, plasma ion assisted deposition method, chemical vapour deposition technique and the atomic layer deposition method any one; Electrode material wherein is the monometallic material, and is a kind of in the monometallic material among W, Pt, Au, Ti, Al, Ag, Cu or the Ni, or it is combined into alloy material.
12) utilize the micro-nano process technology that upper and lower electrode is drawn at last, form phase-change memory storage unit (as shown in figure 12), the micro-nano process technology of employing be in conventional photoetching technique, focused-ion-beam lithography technology, atomic force microscope process technology, electron beam lithography method, extreme ultraviolet photolithographic method, nano impression method or the semiconductor standard processes any.
Architectural feature according to the obtained phase-change memory storage unit of above-mentioned preparation method is: be coated with lower electrode layer on substrate; On bottom electrode, be coated with insulation material layer, have hole in the insulation material layer; Include the open column shape heating electrode material structure that communicates with bottom electrode in the hole; Be coated with insulation material layer on the column heating electrode, include hole in the insulation material layer with column heating electrode alignment; And in column heating electrode hole, contain reversible phase-change material with the insulation material layer hole; On phase-change material layers, be coated with insulation material layer, in insulation material layer, comprise hole, and filled the upper electrode material that communicates with phase-change material within it.
The characteristics of phase-change memory storage unit of the present invention are: phase-change material is incorporated in the heating electrode of open column shape by heat treated way, because microcapillary effect, gas in the nanotube of one end sealing is difficult to discharge, just be sealed in the heating electrode of open column shape by phase-change material, the phase-change memory storage unit structure of Huo Deing has just possessed following advantage like this: 1) annular heating electrode reduces the contact area of electrode and phase-change material greatly; 2) the phase-change material volume that is introduced in the open column shape heating electrode is very little, and also very little with the contact area of heating electrode, is easy to undergo phase transition; 3) under the effect of electric pulse, because temperature raises, the volume expansion in the open column shape heating electrode is compressed phase-change material, makes phase-change material be in high temperature, the hyperbaric environment, is highly susceptible to undergoing phase transition; 4) after the phase-change material in the column heating electrode undergoes phase transition, can further induce other phase-change material to undergo phase transition, thereby reduce the required power consumption of phase transformation greatly.
Description of drawings
Fig. 1 prepares lower electrode layer on substrate
Fig. 2 covers insulation material layer on bottom electrode
Fig. 3 prepares hole in insulation material layer
Fig. 4 fills heating electrode material in hole, and removes the unnecessary heating electrode material of heat-insulating material laminar surface, forms the open column shape heating electrode
Cover insulation material layer on Fig. 5 column heating electrode
Fig. 6 prepares the hole with column heating electrode alignment in insulation material layer
Deposition reversible transition material in the hole of Fig. 7 on the column heating electrode
Fig. 8 carries out annealing in process under atmosphere protection, the partial phase change material is entered in the open tubular column of heating electrode
Fig. 9 prepares heat-insulating material on phase-change material layers
Figure 10 prepares hole in insulation material layer
Figure 11 fills electrode material in hole
Figure 12 draws upper and lower electrode, forms phase-change memory storage unit
Embodiment
Embodiment 1:
A kind of concrete preparation process of phase-change memory storage unit is as follows:
1) is being coated with SiO
2Silicon substrate on adopt direct current magnetron sputtering process to prepare one deck Al lower electrode layer, the SiO of silicon substrate
2The preparation of employing thermal oxidation method, SiO
2The thickness of material is 1000nm.The technological parameter of preparation Al electrode is: background air pressure is 2 * 10
-4Pa, Ar gas air pressure is 0.2Pa during sputter, and sputtering power is 200W, and underlayer temperature is 25 ℃, and film thickness is 400nm.(Fig. 1)
2) on the Al electrode, prepare SiO
2Insulation material layer, used technology are chemical vapour deposition technique, and film thickness is 500nm.(Fig. 2)
3) utilize 0.18 μ m standard technology at SiO
2Prepare hole in the insulation material layer, the diameter of hole is 260nm.(Fig. 3)
4) in hole, utilize chemical vapour deposition technique to fill heating electrode material W, make it to communicate, carry out chemico-mechanical polishing then and remove SiO with bottom electrode Al
2The W that the heat-insulating material laminar surface is unnecessary forms the open column shape heating electrode, and the internal diameter of open tubular column is 160nm.(Fig. 4)
5) on the column heating electrode, cover SiO
2Insulation material layer, the method for employing are chemical vapour deposition technique, and the thickness of film is 100nm.(Fig. 5)
6) utilize 0.18 μ m standard technology at SiO
2Prepare the hole with column heating electrode alignment in the insulation material layer, hole and column heating electrode coaxial line, the diameter of hole is 500nm.(Fig. 6)
7) in hole, deposit Ge
2Sb
2Te
5Phase-change material, the method for employing are direct current magnetron sputtering process, and technological parameter is: background air pressure is 3 * 10
-4Pa, Ar gas air pressure is 0.15Pa during sputter, and sputtering power is 300W, and underlayer temperature is 25 ℃, and film thickness is 400nm.(Fig. 7)
8) carry out annealing in process under the Ar gas shiled, the partial phase change material is entered in the open tubular column of heating electrode, annealing temperature is 550 ℃, and annealing time is 10 minutes.(Fig. 8)
9) at Ge
2Sb
2Te
5Prepare SiO on the phase-change material layers
2Heat-insulating material, the method for employing are sputtering method, and technological parameter is: background air pressure is 2 * 10
-4Pa, Ar gas air pressure is 0.2Pa during sputter, and sputtering power is 200W, and underlayer temperature is 25 ℃, and film thickness is 500nm.(Fig. 9)
10) by uv-exposure and reactive ion etching method at SiO
2Etch hole in the heat-insulating material, the diameter in hole is 1000nm, and the concrete technological parameter of uv-exposure is: photoresist is 6809, and the gluing rotating speed is 4000r/min, the gluing time is 30s, drying-plate is adopted in preceding baking, and temperature is 100 ℃, and the preceding baking time is 3min, uv-exposure power is 4mW, time for exposure is 12s, develops and adopts Tetramethylammonium hydroxide, and developing time is 5s; The concrete technological parameter of reactive ion etching is: etching background air pressure is 1.3 * 10
-3Pa, etching gas are CHF
3With the mist of Ar, its flow is respectively 25 and 25sccm, and etching air pressure is 4Pa, and substrate temperature is 15 ℃, and etching power is 250W, and etch rate is 38.5nm/s.
(Figure 10)
11) in hole, fill electrode material W, make it and Ge
2Sb
2Te
5Phase-change material communicates, and used method is a direct current magnetron sputtering process, and technological parameter is: background air pressure is 2 * 10
-4Pa, Ar gas air pressure is 0.2Pa during sputter, and sputtering power is 200W, and underlayer temperature is 25 ℃, and film thickness is 600nm.
(Figure 11)
12) at last by uv-exposure and reactive ion etching method W electrode etching separately and draw, Al draws bottom electrode, forms phase-change memory storage unit, the width of electrode is 1000nm, and the concrete technological parameter of uv-exposure is: photoresist is 6809, and the gluing rotating speed is 4000r/min, the gluing time is 30s, drying-plate is adopted in preceding baking, and temperature is 100 ℃, and the preceding baking time is 3min, uv-exposure power is 4mW, time for exposure is 12s, develops and adopts Tetramethylammonium hydroxide, and developing time is 5s; The concrete technological parameter of reactive ion etching is: etching background air pressure is 1.3 * 10
-3Pa, etching gas are CF
4And O
2Mist, its flow is respectively 20 and 2sccm, etching air pressure is 10Pa, substrate temperature is 15 ℃, etching power is 200W, etch rate is 32nm/s.(Figure 12)
Present embodiment is by micro-nano process technology and annealing in process, phase-change material is limited in the open tubular column and the hole in the heat-insulating material of heating electrode, like this when electric pulse is operated memory cell, because temperature raises, the gas in the open tubular column and the volume thermal expansion of phase-change material are subjected to the restriction of ambient conditions, make the phase-change material in the electrode open tubular column be under high pressure and the hot environment, can preferentially undergo phase transition, thereby the further phase transformation of the phase-change material of inducing peripheral, under the situation of optimization and control operation window, realize the high speed reversible phase transition process of phase-change material nanoscale around the electrode open tubular column, thereby realize the low pressure of phase-change memory cell, low-power consumption, high-speed functions.
Embodiment 2
W columnar electrode among the embodiment 1 is changed into TiN, and all the other are similar to embodiment 1.
Embodiment 3
The Ge of embodiment 1 and embodiment 2
2Sb
2Te
5Phase-change thin film changes Si into
2Sb
2Te
5Phase-change thin film, all the other are similar with embodiment 2 to embodiment 1.
Embodiment 4
Columnar electrode internal diameter among embodiment 1, embodiment 2 and the embodiment 3 is changed into 50nm, and all the other are similar with embodiment 3 to embodiment 1, embodiment 2.
Embodiment 5
The SiO that is used for perforate among embodiment 1, embodiment 2, embodiment 3 and the embodiment 4
2Adiabatic film changes Si into
3N
4Film, all the other are similar with embodiment 4 to embodiment 1, embodiment 2, embodiment 3.
Claims (10)
1, a kind of phase-change memory storage unit is characterized in that: be coated with lower electrode layer on substrate; On bottom electrode, be coated with insulation material layer, have hole in the insulation material layer; Comprise the open column shape heating electrode material structure that communicates with bottom electrode in the hole; Be coated with insulation material layer on the column heating electrode, comprise hole in the insulation material layer with column heating electrode alignment; And in column heating electrode hole, contain the reversible transition material layer with the insulation material layer hole; On phase-change material layers, be coated with insulation material layer, in insulation material layer, comprise hole, and filled the upper electrode material that communicates with phase-change material within it.
2, by the described phase-change memory storage unit of claim 1, it is characterized in that:
1) diameter of hole is 10-500nm in the described insulation material layer that covers on the bottom electrode;
2) internal diameter of the described open column shape electrode that communicates with bottom electrode is 5-490nm;
3) thickness of the described insulation material layer that covers on the column heating electrode is 10-300nm;
4) described is 10-2000nm with the hole diameter of column heating electrode alignment on the insulation material layer that covers on the column heating electrode;
5) thickness of sediment phase change material layer is 10-500nm in the hole on described column heating electrode;
6) the heat-insulating material layer thickness that covers on described phase-change material layers is 50-500nm.
3, the method for preparation phase-change memory storage unit as claimed in claim 1 or 2 is characterized in that:
1) on substrate, prepares lower electrode layer;
2) on bottom electrode, cover insulation material layer;
3) by the micro-nano process technology, in insulation material layer, prepare hole;
4) in hole, utilize chemical vapour deposition (CVD), ald or physical gas-phase deposite method to fill heating electrode material, make it to communicate, carry out chemico-mechanical polishing then, form the open column shape heating electrode with bottom electrode;
5) on the column heating electrode, cover insulation material layer;
6) in insulation material layer, prepare hole with column heating electrode alignment;
7) deposition reversible transition material layer in the hole on the column heating electrode;
8) under atmosphere protection, carry out annealing in process, the partial phase change material is entered in the open tubular column of heating electrode, in the scope that annealing temperature is in the glass transformation temperature that is higher than phase-change material, be lower than fusion temperature;
9) on phase-change material layers, prepare insulation material layer again;
10) by the micro-nano process technology, in insulation material layer, prepare hole;
11) in hole, fill electrode material, make it to communicate with phase-change material;
12) utilize the micro-nano process technology that upper and lower electrode is drawn at last, form memory cell.
4, by the preparation method of the described phase-change memory storage unit of claim 3, it is characterized in that described substrate be in silicon substrate, glass, GaAs, SiO2, plastics or the crystalline material on silicon chip, the insulating barrier any one.
5, press the preparation method of the described phase-change memory storage unit of claim 3, the preparation that it is characterized in that described electrode material is to adopt thin film preparation process, its method be in sputtering method, evaporation, plasma ion assisted deposition method, chemical vapour deposition technique and the atomic layer deposition method any one; Described electrode material is a kind of in the monometallic material among W, Pt, Au, Ti, Al, Ag, Cu or the Ni, or its alloy material that is combined into.
6, by the preparation method of the described phase-change memory storage unit of claim 3, it is characterized in that method that the preparation of described insulation material layer is adopted be in sputtering method, evaporation, atomic layer deposition method, plasma ion assisted deposition method, chemical vapour deposition technique, metallo-organic decomposition process and the laser assistant depositing method any one; Described insulating material is the mixture of a kind of or at least two kinds of formations in oxide, nitride, carbide, the sulfide.
7, press the preparation method of the described phase-change memory storage unit of claim 3, the preparation that it is characterized in that described filling heating electrode material is to adopt thin film preparation process, is specially in chemical vapour deposition technique, atomic layer deposition method and the physical vaporous deposition any one; Described heating electrode material is a kind of among W, TiN, TiON, GeWN, GeTiN, TiW, GeN or the SiGe.
8, press the preparation method of the described phase-change memory storage unit of claim 3, the method that it is characterized in that the preparation of described phase-change material is to adopt thin film preparation process, in sputtering method, evaporation, Metalorganic Chemical Vapor Deposition, chemical vapour deposition technique and the atomic layer deposition method any one; Described chalcogenide compound is for containing a kind of compound of the 6th major element at least.
9, by the preparation method of the described phase-change memory storage unit of claim 3, it is characterized in that micro-nano process technology that described hole preparation adopted in conventional photoetching technique, focused-ion-beam lithography technology, atomic force microscope process technology, electron beam lithography method, extreme ultraviolet photolithographic method, nano impression method or the semiconductor standard processes any.
10, by the preparation method of the described phase-change memory storage unit of claim 3, it is characterized in that carrying out annealing in process under the atmosphere protection, the partial phase change material is entered in the open tubular column of heating electrode, used protective gas is Ar, N
2, O
2, among He or the Ne any.
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