CN1889285A - Non-volatile memory component based on RbAg4I5 film and producing method thereof - Google Patents
Non-volatile memory component based on RbAg4I5 film and producing method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 45
- 229910002781 RbAg4I5 Inorganic materials 0.000 title 1
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 238000000151 deposition Methods 0.000 claims abstract description 35
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 238000005530 etching Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 124
- 239000000463 material Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 230000008021 deposition Effects 0.000 claims description 27
- 230000004888 barrier function Effects 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 19
- 238000004549 pulsed laser deposition Methods 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010884 ion-beam technique Methods 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000000427 thin-film deposition Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000609 electron-beam lithography Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001259 photo etching Methods 0.000 claims description 2
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
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Abstract
The present invention discloses resistance switch effect based non-volatilisation phase transition memory element physical design preparation method. It contains setting solid electrolyte RbAg 4I5 film between reaction electrode and non - reaction electrode to construct one miniature sandwich structure of memory unit, said memory unit together with substrate and insulating layer all having five layers, depositing single-layer non - reaction electrode on substrate, depositing single-layer insulating layer on non - reaction electrode, and etching one micro pore in it to expose non - reaction electrode, depositing single-layer RbAg 4I5 film on insulating layer, thereon depositing single-layer reaction electrode, respectively leading out leading wire on non - reaction electrode and reaction electrode. Said memory element has advantages of compactness, simple structure, non-volatilisation, rapid read-write, low operating voltage and energy consumption, non - moving part, and nondestructive readout etc.
Description
One, technical field
The invention belongs to microelectronic component and Material Field thereof, but a kind of high density of novel fast reading and writing that is specifically related to be applied to integrated circuit is based on solid electrolyte RbAg
4I
5Non-volatile phase-change memory element and preparation method thereof.
Two, background technology
Since nearly half a century, development of integrated circuits has been followed the prophesy that G.E.Moore proposes substantially: " integrated parts number doubled in per 18 months on the single chip ", that is Moore's Law.When the silicon base CMOS size of devices narrows down to nanometer scale gradually, traditional devices is more and more walked close to the limit of physics and technology.In order to comply with the development trend of integrated circuit technique, to construct novel semiconductor device and must rely on new device simple in structure, as to be easier to realize miniaturization, these memory devices depend on new principle, new structure design, new material and new preparation process.
The two big fundamental systems that constitute computer are storage system and treatment system.The development of memory plays crucial effects to development of computer.At present, the memory of computer employing is divided into volatile memory and nonvolatile memory two big classes.The former mainly comprises dynamic random access memory (DRAM), and they have the advantage of fast reading and writing, but when work extraneous must the continual power supply that provides, thereby bigger energy consumption is arranged when working, and canned data disappears immediately when cutting off the electricity supply.The latter mainly is the magnetic medium memory, because magnetic head and recording medium machinery will take place relatively move in the read-write process, thereby can't realize fast reading and writing.The ferroelectric memory of studying in addition in addition (FeRAM), based on the M-RAM of spin-electronic material etc., they also use as yet in a large number because of some weakness separately.
Three, summary of the invention
1, goal of the invention
The purpose of this invention is to provide a kind of based on solid electrolyte RbAg
4I
5The structural design and preparation method thereof of non-volatile phase-change memory element.
2, technical scheme
A kind of based on solid electrolyte RbAg
4I
5Non-volatile phase-change memory element, the basic configuration that it is characterized in that this memory cell is sandwich structure, namely uses one deck solid electrolyte RbAg
4I
5Film (3) is clipped in to construct between reaction electrode film (4) and the nonreactive electrode film (1) and forms, and this sandwich structure is positioned on the backing material (7), at nonreactive electrode film (1) and solid electrolyte RbAg
4I
5One layer insulating (2) is arranged between the film (3), be carved with micropore (5) at insulating barrier (2), expose nonreactive electrode film (1), and make RbAg
4I
5Film (3) and nonreactive electrode film (1) close contact are at RbAg
4I
5One deck reaction electrode film (4) is arranged on the film (3), and on reaction electrode film (4) and nonreactive electrode film (1), pick out respectively lead-in wire (6).
The structural design main points of above-mentioned non-volatile phase-change memory element comprise:
(1) basic configuration of memory cell is sandwich structure, is about to one deck solid electrolyte RbAg
4I
5 Film 3 is clipped in and is built into a miniature sandwich structure between reaction electrode film 4 and the nonreactive electrode film 1, a mnemon that Here it is, and as a button capacitor, the yardstick of its effective working region can be between 30 nanometers to 10 micron;
(2) this sandwich structure prepares at silicon chip, or quartz glass plate, or the silicon chip lining that thin layer of silicon dioxide covers hangs down;
(3) above-mentioned nonreactive electrode film 1 is platinum (Pt), or gold (Au), and thickness is between 100 nanometers to 1 micron;
(4) in order to control the effective dimensions of memory cell, deposit thickness is the silica membrane insulating barrier 2 of 30 nanometer to 300 nanometers on nonreactive electrode film 1, the etching diameter is the micropore 5 of 30 nanometers to 10 micron on this insulating barrier 2 then, expose nonreactive electrode film 1, the size of this micropore 5 is the yardstick of the effective working region of memory cell;
(5) insulating barrier 2 top deposition solid electrolyte RbAg
4I
5 Film 3, its thickness are 100 nanometer to 500 nanometers, note making RbAg at the be etched position of micropore 5 of insulating barrier 2
4I
5 Film 3 and nonreactive electrode film 1 necessary close contact;
(6) at RbAg
4I
5The top deposit thickness of film 3 is the reaction electrode film 4 of 200 nanometer to 800 nanometers, and its material is silver (Ag) or silver alloy;
(7) pick out the lead-in wire made from spun gold or copper wire 6 respectively by reaction electrode film 4 and nonreactive electrode film 1.The brief introduction of work principle of this novel non-volatile phase-change memory element is as follows:
We have adopted a kind of new material one solid electrolyte RbAg
4I
5 Film 3 is clipped in this film between reaction electrode film 4 (silverskin) and the nonreactive electrode film 1 (platinum film) and is built into a miniature sandwich structure, a mnemon that Here it is.Apply the positive voltage that is higher than certain threshold value at reaction electrode 4, the part silver atoms in the reaction electrode 4 changes silver ion into and enters solid electrolyte RbAg
4I
5 Film 3 also forms the silver-colored line passage of nanoscale, and electricity is led thereupon and risen significantly.Otherwise, applying the positive voltage that is higher than certain threshold value on the nonreactive electrode 1, pt atom can not change platinum ion into and enter solid electrolyte RbA
4I
5 Film 3, and the silver ion in the solid electrolyte 3 will partly change silver atoms into and be deposited on the reaction electrode 4, this causes original nanoscale silver line passage to be disintegrated, and electricity is led thereupon and is descended significantly.The high resistance and low resistance state has here just constituted " 0 " and " 1 " two states in the Boolean algebra.Can realize the high resistance and low resistance state with the voltage that is higher than threshold value (1-3V) pulse of negative or positive, that is " wiping " and " writing ", the resistance that utilization is lower than voltage (0.3-0.5V) the impulsive measurement element of threshold value can realize that then non-destructive reads.We have made novel non-volatile memory component to utilize this principle and structure.Its basic configuration is sandwich structure, and as a button capacitor, yardstick can be between 30 nanometers to 10 micron.Advantage such as it has, and but little, simple in structure, the non-volatile fast reading and writing of volume, operating voltage are low, low energy consumption, movement-less part, non-destructive are read.
Be used to prepare one group of new material of non-volatile phase-change memory element and prepare key technology:
(1) material of the nonreactive electrode film 1 of memory cell is platinum (Pt), or gold (Au), adopts magnetron sputtering, ion beam depositing or pulsed laser deposition preparation;
(2) material of the reaction electrode film 4 of memory cell is silver (Ag) or a silver alloy, adopts the preparation of magnetron sputtering or ion beam depositing or pulsed laser deposition;
(3) silica membrane insulating barrier 2 adopts the radio frequency magnetron sputtering method preparation;
(4) solid electrolyte RbAg
4I
5 Film 3 material preparations are keys of this memory cell material preparation, need the RbAg of synthetic accurate stoicheiometry
4I
5The one-component ceramic target adopts pulsed laser deposition technique to prepare RbAg then
4I
5 Film 3, its preparation process is as follows:
A) RbAg
4I
5One-component ceramic target 10 is to use RbAg
4I
5Powder sintered preparation; Mixture at 400 ℃ of fusing AgI and RbI; Water is quenched into room temperature with mixture; Heat-treat after the block that obtains pulverized, then with RbAg
4I
5The powder static pressure becomes disk, in cabinet-type electric furnace the disk sintering is formed;
B) with RbAg
4I
5One-component ceramic target 10 is fixed on the target platform 11 of deposition film making system of pulse laser (as shown in Figure 2), substrate 7 is fixed on the substrate table 14, resistance-heated furnace 16 is placed in the below of substrate table 14, and they are placed in the growth room 12 of deposition film making system of pulse laser;
C) by interface valve 13 growth room 12 is evacuated down to 0.1Pa with mechanical pump, in growth room 12, feeds protective gas from air vent hole 15 then, and make maintenance 5-15Pa pressure in the growth room 12;
D) be heated by resistive stove 16 heated substrate platforms 14, make backing material 7 temperature be set in 80 ℃;
E) with KrF excimer laser 8, start laser instrument, make laser beam focus on RbAg by quartz glass lens 9
4I
5On the one-component ceramic target 10;
F) RbAg
4I
5Carry out again in-situ annealing after the thin film deposition.
Fig. 3 shows, RbAg
4I
5The X-ray diffraction of single-phase film (XRD) figure.The corresponding RbAg of diffraction maximum among the figure
4I
5Phase, sharp-pointed peak shows RbAg
4I
5Film have a good crystallization state, therefore, the result of XRD proves RbAg
4I
5Single-phase film presents crystalline state and has RbAg
4I
5Phase.
The preparation method of this non-volatile phase-change memory element, its preparation process is as follows:
(a), at silicon chip, or quartz glass plate, or the silicon chip substrate (7) that thin layer of silicon dioxide covers goes up with magnetron sputtering or ion beam depositing or pulsed laser deposition deposition nonreactive electrode film (1), the thickness of its electrode film is between 100 nanometers to 1 micron;
(b), on nonreactive electrode film (1), utilize radio frequency magnetron sputtering method to deposit a layer insulating (2), the material of insulating barrier is a silicon dioxide, its thickness is 30 nanometer to 300 nanometers, use the SiO 2-ceramic target during sputter, the argon gas that with pressure is 5-15Pa is a sputter gas, and underlayer temperature is 80 ℃;
(c), on insulating barrier (2), utilize the focused particle beam etching method, or the electron beam lithography method, or photoetching process processes the micropore (5) that diameter is 30 nanometers-10 micron, exposes the nonreactive electrode film (1) of bottom;
(d), cover on the insulating barrier (2) that processes micropore to the metal mask plate of 0.1mm hole, the hole of mask plate is aimed at the hole on the insulating barrier (2) with to be carved with diameter be 0.5mm;
(e), will put into the pulsed laser deposition chamber through the substrate (7) that above-mentioned steps (a), (b), (c), (d) are coated with mask, utilize pulsed laser deposition technique deposition solid electrolyte RbAg
4I
5Film (3), this film fill up micropore (5) fully and form a boss in mask plate hole scopes, and the height of platform is the 100-500 nanometer, makes RbAg
4I
5Film (3) and nonreactive electrode film (1) close contact;
(f), by metal mask plate with pulse laser sediment method or magnetically controlled sputter method deposition reaction electrode film (4) on above-mentioned boss, its thickness is 200 nanometer to 800 nanometers, uses silver or silver alloy target during deposition, is 10 in growth room (12)
-4The Pa low vacuum, substrate (7) temperature is 80 ℃;
(g), in-situ annealing was carried out 1 hour in 150 ℃ in reaction electrode film (4) deposition back;
(h), pick out lead-in wire (6) respectively by reaction electrode film (4) and nonreactive electrode film (1).
Above-mentioned solid electrolyte RbAg
4I
5The thin film technology method, the proportioning of AgI and RbI mixture is 80mol% AgI and 20mol% RbI in step (a), it is rear at 150 ℃ of lower heat treatment 14h, with RbAg that block is pulverized
4I
5Powder normal temperature static pressure under 14MPa becomes the disk of Φ 21 * 4mm, in electric furnace disk is made RbAg at 150 ℃ of lower sintering 8h
4I
5One-component ceramic target (10).
Above-mentioned solid electrolyte RbAg
4I
5The thin film technology method, at the KrF excimer laser (8) described in the step (e), its wavelength 248nm, pulse width 30ns, single pulse energy 10-500mJ, energy density is 2.0 J/cm
2
Above-mentioned solid electrolyte RbAg
4I
5The thin film technology method, RbAg in step (f)
4I
5The in-situ annealing temperature of film is 150 ℃, anneals 1 hour.
Above-mentioned nonreactive electrode film (1), its material is platinum or gold.
Above-mentioned reaction electrode film (4), its material is silver or silver alloy.
Above-mentioned lead-in wire (6), its material is made with spun gold or copper wire.
Above-mentioned protective gas is argon gas or nitrogen.
The performance test of this novel non-volatile phase-change memory element:
The instrument that the memory cell that makes is carried out performance test is: Keithley 236 source measurement units; Angilent 33120A function; Angilent 54845A oscilloscope; D/Max-RA type X-ray diffractometer.Main test component to one-period change the response of voltage and device to read-write-read-response of erasing voltage periodic signal.
3, beneficial effect
(1) on the reaction electrode film 4 of this memory cell, applies a positive voltage, when this voltage reaches certain threshold value, memory cell changes low resistance state suddenly into by high-resistance state, the voltage that applies progressively reduces and becomes negative value, the resistance of memory cell remains on low resistance state, the absolute value that applies negative voltage on reaction electrode film 4 reaches certain threshold value, and memory cell changes high-resistance state suddenly into by low resistance state.Fig. 4 has at length shown RbAg
4I
5Memory cell is to the response of voltage, and namely making alive is also measured response current simultaneously with the situation of voltage change.As can be seen from the figure: from the e point to a point, memory cell presents high-impedance state (resistance is in the megohm magnitude); When surpassing a point, device resistance presents transition, response current increases suddenly, present a kind of linear voltage-current relationship from the b point to the c point, memory cell becomes low resistance state (resistance is hundred ohm of magnitudes), from the c point, the memory cell response presents negative differential resistance, get back to again high-impedance state to d point device, keep high-impedance state constant from the d point to e point device, the ratio of height resistance state resistor/resistance value is 10
4, this test result explanation RbAg
4I
5Memory cell has significant switching effect, and the ratio of resistance is up to 10 under its open and close state
4Magnitude, this is very beneficial for reading of memory elements.
(2) owing to the above-mentioned good switching characteristic of memory cell, it has the function that reads-write-read-wipe of nonvolatile memory fully.We might as well be defined as low resistance state " writing " or " 1 ", high-resistance state are defined as " wiping " or " 0 "; Fig. 5 show this novel non-volatile phase-change memory element to read-write-read-response of erasing voltage periodic signal, when reading pulse a and be added on the element, the response current of memory cell is zero substantially, be in high-resistance state, writing when pulse b is applied on the memory cell makes device switch to low resistance state, bigger response current (1.5mA) appears simultaneously, next immediately when reading pulse c and being added on the memory cell response current of element be that (corresponding resistance is 10 to 0.8mA
2Ohm), the result that erasing pulse d acts on memory cell makes element occur switching to high-resistance state behind the big electric current of a transient state; Thereby to the read pulse no current response of next cycle following closely (corresponding resistance is for being at least 10
3Ohm), this explanation. reading-write-read-effect of erasing voltage periodic signal under, this novel non-volatile phase-change memory element has the basic function of nonvolatile memory fully, test shows element switch number of times can reach 10
3Inferior, the memory retention time can reach 200 hours.
(3) because the read pulse voltage of this novel non-volatile phase-change memory element is starkly lower than the write/erase pulse voltage, it does not change canned data in the device when reading, thereby is that a kind of non-destructive is read memory elements.
(4) because this novel non-volatile phase-change memory element only has two lead-out wires, all read-write-read-erase operation all finished by these two lead-out wires by the signal of telecommunication, without any the mechanical movement contact, it has characteristics simple in structure and can realize fast reading and writing.
(5) because the basic principle of this novel non-volatile phase-change memory element stored information is the high resistance and low resistance attitude that phase transformation causes in the device, and not needing during information stores provides any energy supplement to it, it is a kind of nonvolatile memory.
Four, description of drawings
Fig. 1: the structural representation of memory cell.
1-nonreactive electrode film; The 2-silicon dioxide insulating layer; 3-RbAg
4I
5Film; 4-reaction electrode film; The micropore of etching on the 5-insulating barrier; 6-reaction electrode film, nonreactive electrode film lead-in wire; The 7-backing material.
Fig. 2: preparation RbAg
4I
5The structural representation of the pld (pulsed laser deposition) growing system of film.
The 8-KrF excimer laser; The lens of 9-laser focusing; 10-RbAg
4I
5The one-component ceramic target; 11-target platform; The 12-growth room; The interface valve of 13-mechanical pump and molecular pump; The 7-backing material; The 14-substrate table; The 15-air vent valve; The 16-resistance-heated furnace.
Fig. 3: RbAg
4I
5The X-ray diffractogram of film.The x axle is the angle of diffraction 2 θ (unit is degree) among the figure, and the y axle is the diffracted ray relative intensity.Show that film is single-phase RbAg
4I
5Structure.
Fig. 4: the voltage-current characteristic of memory cell, wherein the x axle is represented the suffered voltage of device (unit is volt), the y axle is represented the response current (unit is ampere) of device.The process that voltage applies is from 0V to+0.3V, to 0V, to-0.3V, to 0V.Voltage signal is the step pattern, and step width is about 100ms.A, b, c, d, e refer to measure the point on the curve.
Fig. 5: the read write attribute of memory cell, wherein the x axle represents the time (unit is second), (a) the y axle among the figure is the suffered voltage signal of device (unit is volt); (b) the y axle among the figure is the current signal (unit is milliampere) of response device.A, b, c, d refer to read pulse, write pulse, read pulse, erasing pulse respectively.
Five, embodiment
(1), on silicon chip substrate 7 with pulsed laser deposition deposition nonreactive electrode film 1, its material is a platinum, the thickness of nonreactive electrode film 1 is 200 nanometers;
(2), on nonreactive electrode film 1, utilize radio frequency magnetron sputtering method to deposit a layer insulating 2, the material of insulating barrier is a silicon dioxide, its thickness is 100 nanometers;
(3), in insulating barrier 2, utilize the focused particle beam etching method, processing diameter is the micropore 5 of 200 nanometers, exposes the nonreactive electrode film 1 of bottom;
(4), be that the metal mask plate of 0.5mm hole covers on the substrate that processes micropore 5 with being carved with diameter, the hole of mask plate is aimed at the hole on the substrate;
(5), will put into the pulsed laser deposition chamber through the substrate 7 that above-mentioned steps (a), (b), (c), (d) are coated with mask, utilize pulsed laser deposition technique deposition solid electrolyte RbAg
4I
5Film 3, this film fill up micropore 5 fully and form a boss in mask plate hole scopes, and the height of platform is 300 nanometers, makes RbAg
4I
5Film (3) and nonreactive electrode film (1) close contact;
(6), by metal mask plate with pulse laser sediment method, on above-mentioned boss deposition reaction electrode film 4, its material be silver-colored, thickness is 200 nanometers, is 10 in the growth room 12
-4The Pa low vacuum, substrate 7 temperature are 80 ℃;
(7), in-situ annealing was carried out 1 hour in 150 ℃ in reaction electrode film 4 deposition backs;
(8), pick out spun gold lead-in wire 6 by reaction electrode film 4 and nonreactive electrode film 1 respectively at last.
(1), on quartz glass plate substrate 7 with magnetron sputtering method deposition nonreactive electrode film 1, its material be golden, the thickness of nonreactive electrode film 1 is 1 micron;
(2), on nonreactive electrode film 1, utilize radio frequency magnetron sputtering method to deposit a layer insulating 2, the material of insulating barrier is a silicon dioxide, and its thickness is 200 nanometers, uses the SiO 2-ceramic target during sputter, the argon gas that with pressure is 10Pa is a sputter gas, and the lining low temperature is 80 ℃;
(3), utilizing the electron beam lithography method to process diameter in insulating barrier 2 is 10 microns micropore 5, exposes the golden nonreactive electrode film 1 of bottom;
(4), be that the metal mask plate of 0.4mm hole covers on the substrate that processes micropore 5 with being carved with diameter, the hole of mask plate is aimed at micropore 5;
(5), will put into the pulsed laser deposition chamber through the substrate 7 that above-mentioned steps (a), (b), (c), (d) are coated with mask, utilize pulsed laser deposition technique deposition solid electrolyte RbAg
4I
5Film 3, this film fill up micropore 5 fully and form a boss in mask plate hole scopes, and the height of platform is 300 nanometers, makes RbAg
4I
5Film (3) and nonreactive electrode film (1) close contact;
(6), by metal mask plate with magnetically controlled sputter method deposition reaction electrode film 4 on above-mentioned boss, its material is a silver alloy, thickness is 600 nanometers, is 10 in the growth room 12
-4The Pa low vacuum, substrate 7 temperature are 80 ℃;
(7), in-situ annealing was carried out 1 hour in 150 ℃ in reaction electrode film 4 deposition backs;
(8), pick out copper wire lead-in wire 6 by reaction electrode film 4 and nonreactive electrode film 1 respectively at last.
(1) RbAg
4I
5One-component ceramic target (10) is to use RbAg
4I
5Powder sintered preparation: at the mixture of 400 ℃ of fusing 80mol% AgI and 20mol% RbI, water is quenched into room temperature with mixture, heat-treats 14h after the block that obtains is pulverized under 150 ℃, then with RbAg
4I
5Powder normal temperature static pressure under 14MPa becomes the disk of Φ 21 * 4mm, in cabinet-type electric furnace disk is made at 150 ℃ of lower sintering 8h;
(2) with RbAg
4I
5One-component ceramic target (10) is fixed on the target platform (11) of deposition film making system of pulse laser, substrate (7) is fixed on the substrate table (14), resistance-heated furnace (16) is placed in the below of substrate table (14), and they are placed in the growth room (12) of deposition film making system of pulse laser;
(3) by interface valve (13) growth room (12) are evacuated down to 0.1Pa with mechanical pump, in growth room (12), feed argon gas from air vent hole (15) then, and make maintenance 10Pa pressure in the growth room (12);
(4) be heated by resistive stove (16) heated substrate platform (14), make substrate (7) temperature be set in 80 ℃;
(5) with KrF excimer laser (8), start laser instrument, make laser beam pass through quartz glass lens (9) and focus on RbAg
4I
5On the one-component ceramic target (10);
(6) solid electrolyte RbAg
4I
5Under 150 ℃, carried out in-situ annealing 1 hour after the thin film deposition.
Embodiment 4. is for the preparation of the solid electrolyte RbAg of non-volatile phase-change memory element
4I
5The preparation method of thin-film material, its preparation process is as follows:
(1) RbAg
4I
5One-component ceramic target (10) is to use RbAg
4I
5Powder sintered preparation: at the mixture of 400 ℃ of fusing 80mol% AgI and 20mol% RbI, water is quenched into room temperature with mixture, heat-treats after the block that obtains is pulverized, then with RbAg
4I
5Powder normal temperature static pressure under 14MPa becomes the disk of Φ 21 * 4mm, in cabinet-type electric furnace disk is made at 150 ℃ of lower sintering 8h;
(2) with RbAg
4I
5One-component ceramic target (10) is fixed on the target platform (11) of deposition film making system of pulse laser, substrate (7) is fixed on the substrate table (14), resistance-heated furnace (16) is placed in the below of substrate table (14), and they are placed in the growth room (12) of deposition film making system of pulse laser;
(3) by air vent hole (13) growth room (12) are evacuated down to 0.1Pa with vacuum pump, in growth room (12), feed nitrogen from air vent hole (15) then, and make maintenance 10Pa pressure in the growth room (12);
(4) be heated by resistive stove (16) heated substrate platform (14), make substrate (7) temperature be set in 80 ℃;
(5) with KrF excimer laser (8), start laser instrument, make laser beam pass through quartz glass lens (9) and focus on RbAg
4I
5On the one-component ceramic target (10);
(6) solid electrolyte RbAg
4I
5Carried out in-situ annealing 1 hour at 150 ℃ after the thin film deposition.
Claims (10)
1, a kind of based on solid electrolyte RbAg
4I
5Non-volatile phase-change memory element, the basic configuration that it is characterized in that this memory cell is sandwich structure, namely uses one deck solid electrolyte RbAg
4I
5Film (3) is clipped in to construct between reaction electrode film (4) and the nonreactive electrode film (1) and forms, and this sandwich structure is positioned on the backing material (7), at nonreactive electrode film (1) and solid electrolyte RbAg
4I
5One layer insulating (2) is arranged between the film (3), be carved with micropore (5) at insulating barrier (2), expose nonreactive electrode film (1), and make RbAg
4I
5Film (3) and nonreactive electrode film (1) close contact are at RbAg
4I
5One deck reaction electrode film (4) is arranged on the film (3), and on reaction electrode film (4) and nonreactive electrode film (1), pick out respectively lead-in wire (6).
2, memory cell according to claim 1 is characterized in that described solid electrolyte RbAg
4I
5Film (3) is that its preparation process is as follows with the pulsed laser deposition preparation:
(a) RbAg
4I
5One-component ceramic target (10) is to use RbAg
4I
5Powder sintered preparation: at the mixture of 400 ℃ of fusing AgI and RbI, water is quenched into room temperature with mixture, heat-treats after the block that obtains is pulverized, then with RbAg
4I
5The powder static pressure becomes disk, in cabinet-type electric furnace the disk sintering is formed;
(b) with RbAg
4I
5One-component ceramic target (10) is fixed on the target platform (11) of deposition film making system of pulse laser, substrate (7) is fixed on the substrate table (14), resistance-heated furnace (16) is placed in the below of substrate table (14), and they all are placed in the growth room (12) of deposition film making system of pulse laser;
(c) by interface valve (13) growth room (12) are evacuated down to 0.1Pa with mechanical pump, in growth room (12), feed protective gas from air vent hole (15) then, and make maintenance 5-15Pa pressure in the growth room (12);
(d) be heated by resistive stove (16) heated substrate platform (14), make substrate (7) temperature be set in 80 ℃;
(e) with KrF excimer laser (8), start laser instrument, make laser beam pass through quartz glass lens (9) and focus on RbAg
4I
5On the one-component ceramic target (10);
(f) solid electrolyte RbAg
4I
5Carry out again in-situ annealing after the thin film deposition.
3, a kind of method for preparing the described non-volatile phase-change memory element of claim 1, its preparation process is as follows:
(a), at silicon chip, or quartz glass plate, or the silicon chip substrate (7) that thin layer of silicon dioxide covers goes up with magnetron sputtering or ion beam depositing or pulsed laser deposition deposition nonreactive electrode film (1), its thickness is between 100 nanometers to 1 micron;
(b), on nonreactive electrode film (1), utilize radio frequency magnetron sputtering method to deposit a layer insulating (2), the material of insulating barrier is a silicon dioxide, its thickness is 30 nanometer to 300 nanometers, use the SiO 2-ceramic target during sputter, the argon gas that with pressure is 5-15Pa is a sputter gas, and underlayer temperature is 80 ℃;
(c), on insulating barrier (2), utilize the focused particle beam etching method, or the electron beam lithography method, or photoetching process processes the micropore (5) that diameter is 30 nanometers-10 micron, exposes the nonreactive electrode film (1) of bottom;
(d), cover on the insulating barrier (2) that processes micropore to the metal mask plate of 0.1mm hole, the hole of mask plate is aimed at micropore (5) with to be carved with diameter be 0.5mm;
(e), the substrate (7) that will be coated with metal mask plate after above-mentioned steps (a), (b), (c), (d) process successively puts into the pulsed laser deposition chamber, utilizes pulsed laser deposition technique deposition solid electrolyte RbAg
4I
5Film (3), this film fill up micropore (5) fully and form a boss in mask plate hole scopes, and the height of platform is the 100-500 nanometer, makes RbAg
4I
5Film (3) and nonreactive electrode film (1) close contact;
(f), by metal mask plate with pulse laser sediment method or magnetically controlled sputter method deposition reaction electrode film (4) on above-mentioned boss, its thickness is 200 nanometer to 800 nanometers, uses silver or silver alloy target during deposition, is 10 in growth room (12)
-4The Pa low vacuum, substrate (7) temperature is 80 ℃;
(g), in-situ annealing was carried out 1 hour in 150 ℃ in reaction electrode film (4) deposition back;
(h), pick out lead-in wire (6) respectively by reaction electrode film (4) and nonreactive electrode film (1).
4, solid electrolyte RbAg according to claim 2
4I
5The thin film technology method is characterized in that the proportioning of AgI and RbI mixture is 80mol% AgI and 20mol% RbI in step (a), after block is pulverized at 150 ℃ of lower heat treatment 14h, with RbAg
4I
5Powder normal temperature static pressure under 14MPa becomes the disk of Φ 21 * 4mm, in electric furnace disk is made RbAg at 150 ℃ of lower sintering 8h
4I
5One-component ceramic target (10).
5, solid electrolyte RbAg according to claim 2
4I
5The thin film technology method is characterized in that at the protective gas described in the step (c) be argon gas or nitrogen.
6, solid electrolyte RbAg according to claim 2
4I
5The thin film technology method is characterized in that at the KrF excimer laser (8) described in the step (e), its wavelength 248nm, and pulse width 30ns, single pulse energy 10-500mJ, energy density is 2.0J/cm
2
7, solid electrolyte RbAg according to claim 2
4I
5The thin film technology method is characterized in that RbAg in step (f)
4I
5The in-situ annealing temperature of film is 150 ℃, anneals 1 hour.
8, the preparation method of non-volatile phase-change memory element according to claim 3 is characterized in that at the described nonreactive electrode film of step (a) (1), its material is platinum or gold.
9, the preparation method of non-volatile phase-change memory element according to claim 3 is characterized in that at the described reaction electrode film of step (f) (4), its material is silver or silver alloy.
10, the preparation method of non-volatile phase-change memory element according to claim 3 is characterized in that its material is made with spun gold or copper wire at the described lead-in wire of step (h) (6).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107881472A (en) * | 2017-11-23 | 2018-04-06 | 鲁东大学 | A kind of CsPbI3The preparation method of film |
| CN113532702A (en) * | 2021-09-14 | 2021-10-22 | 江苏集萃脑机融合智能技术研究所有限公司 | Pressure sensor with memory function |
| CN114429970A (en) * | 2022-01-25 | 2022-05-03 | 中国电子科技集团公司第五十八研究所 | Preparation method and structure of anti-radiation atomic switch device structure |
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| US5136478A (en) * | 1990-08-03 | 1992-08-04 | Quadri Electronics Corporation | Solid electrolyte capacitor and method of making |
| US5161094A (en) * | 1990-08-03 | 1992-11-03 | Quadri Electronics Corporation | Solid electrolyte capacitor and method of making |
| US5047899A (en) * | 1990-08-03 | 1991-09-10 | Quadri Electronics Corporation | Solid electrolyte capacitor and method of making |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107881472A (en) * | 2017-11-23 | 2018-04-06 | 鲁东大学 | A kind of CsPbI3The preparation method of film |
| CN113532702A (en) * | 2021-09-14 | 2021-10-22 | 江苏集萃脑机融合智能技术研究所有限公司 | Pressure sensor with memory function |
| CN113532702B (en) * | 2021-09-14 | 2021-11-26 | 江苏集萃脑机融合智能技术研究所有限公司 | Pressure sensor with memory function |
| CN114429970A (en) * | 2022-01-25 | 2022-05-03 | 中国电子科技集团公司第五十八研究所 | Preparation method and structure of anti-radiation atomic switch device structure |
| CN114429970B (en) * | 2022-01-25 | 2023-04-07 | 中国电子科技集团公司第五十八研究所 | Preparation method and structure of anti-radiation atomic switch device structure |
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