CN105293451B - Nonequilibrium state chalcogenide, film and preparation method thereof - Google Patents
Nonequilibrium state chalcogenide, film and preparation method thereof Download PDFInfo
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- CN105293451B CN105293451B CN201510753365.6A CN201510753365A CN105293451B CN 105293451 B CN105293451 B CN 105293451B CN 201510753365 A CN201510753365 A CN 201510753365A CN 105293451 B CN105293451 B CN 105293451B
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Abstract
The invention provides a kind of nonequilibrium state chalcogenide, film and preparation method thereof, belongs to memory body chip material technical field.The chemical molecular formula formula of the nonequilibrium state chalcogenide is XY4, wherein Y element is the chalcogen of high volatile in the periodic table of elements.X element and Y element are formed into nonequilibrium state compound by vacuum melting and hot pressed sintering.Further, it is also possible to which the nonequilibrium state chalcogenide is made as into film by plasma sputtering, the film can have outstanding electric property and stability as the critical material of the switch element of memory body chip of new generation.
Description
Technical field
The present invention relates to field a new generation memory body chip material technical field, in particular to a kind of nonequilibrium state
The preparation method of chalcogenide and its film.
Background technology
In non-volatility memory chip of new generation (Non-Volatile Memory) research and development, sulfur family member
Plain compound is to belong to one of most to be paid attention to.Chalcogenide compound shows non-linear current-voltage (I-V Curve) property
Can, under the driving of electric current, extremely fast voltage conversion can occur between 10ns~100ns for the film of this material,
To represent binary digit 0 or 1, so as to reach the purpose of information storage read/write.The switching of this 0/1 state, it is necessary to one
The on-off of individual high speed, it is referred to as Ovonic Threshold Switch (abbreviation OTS).At present, usually using chalcogen
Compound includes GeSe2、GeS2、As2Se3、As2Te3Deng.All it is the Binary-phase according to coherent element when making above-claimed cpd
Figure forms stable, equilibrium state compound.However, the material OTS performance requirements of phase change memory chip are very high, it is above-mentioned
Some compounds can not fully meet requirement of the chip to material electrical property.And nonequilibrium state chalcogenide compound is found to have
Have as the comparatively ideal performance characteristics of OTS materials.It is fewer but to make the research of the chalcogenide of nonequilibrium state, skill
Art difficulty is high, and immature.The nonequilibrium state chalcogenide that existing method makes is unstable, in appropriate exterior power
Decomposition is easily produced under the conditions of, so as to limit its extensive use in non-volatility memory chip field.
The content of the invention
It is steady to be formed it is an object of the invention to provide the preparation method of a kind of nonequilibrium state chalcogenide and its film
Fixed nonequilibrium state chalcogenide, improves its material and electric property, so as to can be in the non-volatile memory of a new generation
It is widely used in chip.
Technical solution of the present invention is as follows：
In a first aspect, it is XY to be used to prepare chemical molecular formula the invention provides one kind4Nonequilibrium state chalcogenide
Method, Y is chalcogen, it is characterised in that be the described method comprises the following steps：
1) by X element and Y element according to Y element relative to the part by weight of X element than the preferable ratio required by molecular formula
The weight ratio of example high 10%~20% is mixed, and is then placed them into vacuum equipment, wherein in the vacuum equipment
Vacuum is 1.0 × 10-3Pa~5.0 × 10-3Pa；
2) vacuum equipment is heated, so that X element and Y element become molten state, then makes X element and Y members
Element reacts under constant temperature；
3) the liquefied mixture fast cooling that after completion of the reaction, will be made up of in the vacuum equipment X element and Y element
To room temperature, to obtain stable nonequilibrium state chalcogenide.
Preferably, the temperature for the mixture being made up of in the step 2) X element and Y element is 700 DEG C~1200 DEG C, is risen
Warm speed is 150 DEG C/h~200 DEG C/h, and the isothermal reaction time is 3~4 hours.
Preferably, the step 2) is further comprising the steps of：React same under constant temperature with Y element making X element
When, the vacuum equipment is vibrated, vibration frequency is 0.5~1Hz.
Preferably, the rate of temperature fall in the step 3) is 10 DEG C~15 DEG C/min.
Second aspect, the formula prepared present invention also offers a kind of method as described in any of the above-described is XY4It is non-
Equilibrium state chalcogenide, the nonequilibrium state chalcogenide include GeSe4、GeS4、CuS4、CuSe4、GeTe4、ZnSe4。
The third aspect, present invention also offers non-flat made of a kind of nonequilibrium state chalcogenide using above-mentioned preparation
Weigh state chalcogenide film.
Fourth aspect, present invention also offers a kind of side for being used to make above-mentioned nonequilibrium state chalcogenide film
Method, comprise the following steps：
A) described method makes stable nonequilibrium state chalcogenide according to a first aspect of the present invention；
B the nonequilibrium state chalcogenide) is handled by the method for powder metallurgy, to obtain sputtering target material；
C) by target described in plasma sputtering, so as to which the nonequilibrium state chalcogenide for forming stable in substrate is thin
Film.
Preferably, step B) it is further comprising the steps of：Powder is made in the nonequilibrium state chalcogenide of the stabilization of preparation；
It is 1 × 10 in vacuum-3Pa~3 × 10-3Pa, temperature are 280 DEG C~400 DEG C, and pressure sinters under conditions of being 400~600 tons
High density material is made in the powder 2.8~3 hours, cooling；Target is made in obtained high density material.
Preferably, rate of temperature fall during cooling is 80~130 DEG C/h.
Preferably, step C) in the plasma sputtering condition be：The nonequilibrium state chalcogenide compound target
The temperature on material surface is not higher than 100 DEG C, and the negative electrode and substrate in sputter chamber are not higher than 10 DEG C of circulating water with temperature, cloudy
The Sputtering power density of pole is not higher than 1.25W/cm2, the thickness of target is less than 5 millimeters.
Beneficial effects of the present invention：
The invention provides a kind of nonequilibrium state chalcogenide, its thin-film material has excellent material and electrical property,
Had broad application prospects in the non-volatility memory chip field of a new generation.In addition, nonequilibrium state chalcogenide with
The periphery material of memory body chip has preferable matching, compatibility good, is remarkably improved the performance of memory body chip of future generation
And reliability.Present invention also offers a kind of preparation method of nonequilibrium state chalcogenide, the preparation method overcomes making
The problem of stability difference is decomposed during nonequilibrium state chalcogenide, can be stabilized, to being stablized at room temperature
And excellent performance memory body chip manufacturing used in switching material there is special meaning.
The invention provides a kind of nonequilibrium state chalcogenide film, the film can be used as the key of memory body chip
On-off component OTS, it has very high ON/OFF speed, and the fast read/write of information, and the memory body core of longer life can be achieved
Piece.Present invention also offers a kind of preparation method of above-mentioned nonequilibrium state chalcogenide film, this method is simple to operate, can make
Stable nonequilibrium state chalcogenide is made, can effectively prevent nonequilibrium state chalcogenide from occurring in use
The problem of decomposition.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below by embodiment it is required use it is attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the nonequilibrium state chalcogenide GeSe that inventive embodiments 1 provide4Preparation method flow chart；
Fig. 2 is the nonequilibrium state chalcogenide GeSe that inventive embodiments 2 provide4The preparation method flow chart of film.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
Part of the embodiment of the present invention, rather than whole embodiments.The present invention implementation being generally described and illustrated herein in the accompanying drawings
The component of example can be configured to arrange and design with a variety of.Therefore, the reality of the invention to providing in the accompanying drawings below
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Embodiment 1
Present embodiments provide a kind of nonequilibrium state chalcogenide GeSe4, the nonequilibrium state chalcogenide by with
Lower section method is made：
First, Se/Ge is put into a high-purity quartz container according to weight than 4.8,.Quartz ampoule is evacuated, and makes
Its vacuum reaches 3.0x10-3Pa, it is then that the one end open of quartz ampoule is closed, make the close of interior one high vacuum of formation of quartz ampoule
Close space.The raising of vacuum advantageously reduces foreign gas in quartz ampoule, avoids the various elements such as O in air2, N2, or
Person H2Etc. being mixed into product.By improving the vacuum in quartz ampoule, final nonequilibrium state GeSe can be improved4Product it is pure
Degree.
Secondly, closed quartz ampoule is put into firing equipment, such as resistance-heated furnace, then carrying out heating to quartz ampoule makes Ge
Reacted with Se into molten state, complete liquefied Ge and Se under constant temperature.Preferably, firing rate control 180 DEG C/it is small
When, the temperature for making Ge and Se mixtures is 860 DEG C.Under conditions of 860 DEG C, Ge and Se are sufficiently mixed, reacted, and form melting
Liquid.It is incubated 3.2 hours at such a temperature.In order to enable Ge and Se fully to react, during incubation, quartz ampoule is put
Put on a device that mechanical can be rocked, rocked with 0.5Hz frequency.By vibration, Ge and Se elements carry out equal
React evenly.
Again, after fully having reacted 3.2 hours under conditions of above-mentioned closed, high temperature and condition of high vacuum degree, cut-out electricity
Hinder the power supply of heating furnace.Quartz ampoule is taken out into body of heater, the air of room temperature is then blown on quartz ampoule periphery, it is complete by convection heat transfer' heat-transfer by convection
Into fast cooling, cooling rate is 12 DEG C/min.Quick cooling can reduce the diffusion velocity of Ge atoms and Se atoms so that
Its atom rapidly " is solidified ".After temperature drops to room temperature, solid is taken out from quartzy tubular container, produces the non-flat of stabilization
The state that weighs GeSe4。
The fast cooling of quartz ampoule promotes the fast cooling of Ge and Se compounds, advantageously forms stable nonequilibrium state
GeSe4.Decline because index (Arrhenius equations) is presented as temperature reduces in the diffusion velocity of Se atoms and Ge atoms,
Therefore Ge, Se atom in quartz ampoule do not have enough dynamic conditions and form the stable phase of equilibrium state to complete to spread, combine.
Embodiment 2
Present embodiments provide a kind of nonequilibrium state chalcogenide GeSe4Film, the nonequilibrium state chalcogenide
GeSe4Film is made by following methods.
The first step, the preparation method provided according to embodiment 1 make stable nonequilibrium state GeSe4。
Second step, the nonequilibrium state GeSe by making4It is made as target.
By the nonequilibrium state GeSe of making4It is positioned in the vapor tight tank full of argon gas, hermetically sealed can is then positioned over planet
Ball mill grinding is into powder.Preferably, powder size control is in 75 microns.
Secondly, high density nonequilibrium state GeSe is made4Bulk.
The powder being ground into is positioned in the graphite jig of high-purity, graphite jig is then put into hot press cavity
It is interior, and the cavity of hot press is pumped into 1.2 × 10-3Pa vacuums.The chamber of hot press is heated, makes the chamber inner pressure of hot press
Power reach 500 tons, nonequilibrium state GeSe in the chamber of hot press4The temperature of powder rises to 285 DEG C.In 285 DEG C, 500 tons of bars
Maintained 2.8 hours under part, make nonequilibrium state GeSe4Powder densified sintering product at the temperature and condition of high voltage.By reducing powder
Particle diameter, the density of bulk can be improved, greatly improve the consistency of material, so as to reduce the issuable sky of material internal
Cave.
The chamber inner high voltage state of heating power supply and hot press is released after vacuum hotpressing, the graphite jig into cavity is blown into
The nitrogen of room temperature.Nonequilibrium state GeSe in graphite jig4So that averagely 120 DEG C of speed cooling lands vertically to room temperature per hour.It is non-
Equilibrium state GeSe4After being cooled to room temperature, graphite jig is taken out out of hot press cavity, then by nonequilibrium state GeSe4Depart from graphite
Mould, that is, obtain according to GeSe4The nonequilibrium state bulk of molecular formula ratio.
3rd step, by GeSe4Bulk is made as stable nonequilibrium state chalcogenide film by sputtering.
First, by GeSe4Bulk is processed into size target, the present embodiment corresponding to sputtering equipment dorsulum by grinding machine
In, the target is round pie, its a diameter of 125mm, thickness 5mm.
Secondly, GeSe4Target is installed in plasma chamber body and sputtered, so as to form GeSe in sputtering substrate4
Film, utilize the GeSe4Film can be made as the crucial OTS films of memory body chip.In the present embodiment, sputtering equipment splashes
Power is penetrated as 150 watts, the electrode and substrate of sputter chamber are both provided with the recirculated cooling water temperature-controlling system of active, the temperature of cooling water
Degree is arranged to 10 DEG C.
Sputtering prepares nonequilibrium state chalcogenide GeSe4The matter that temperature control in thin-film process is formed to final film
Measure particularly significant, therefore, it is necessary to control the temperature of film in sputtering target material and substrate, caused non-equilibrium with preventing temperature too high
The GeSe of state4Decomposition is produced, so as to form equilibrium state compound.
The temperature control of target material surface：During sputtering, the temperature of target material surface is of a relatively high in sputtering chamber, can
So that the GeSe of nonequilibrium state can be caused4Atomic ratio occur deviate and form the GeSe of equilibrium state2.Therefore, it is necessary to enter trip temperature
Control, so that GeSe4Target and the GeSe of the formation in substrate4Film is able to maintain that the atomic ratio of nonequilibrium state.Based on upper
Consideration is stated, it is necessary to make GeSe4Target and substrate will keep relatively low temperature, avoid nonequilibrium state GeSe4Following reactions occurs
Formula (1) is reacted, and so as to maintain the atomic ratio of Ge and Se in OTS film, GeSe4 films is sent out on memory body chip OTS
Wave its unique performance.
GeSe4→GeSe2+Se2 (1)
In GeSe4In the sputter procedure of target, sputtering target material is in the presence of plasma Ar+, GeSe4Target material surface
Temperature can raise, but in order to maintain nonequilibrium state GeSe4It is relatively stable, target material surface temperature is preferably controlled in 100 DEG C
Below.To reach this purpose, there is following approach：
1st, the power density of sputter chamber electrode is controlled, the Sputtering power density of target material surface is in 1.25W/cm2Under.
2nd, the thickness of target should be controlled under 5mm.Due to chalcogenide compound GeSe4Thermal conductivity factor it is small, splash
Caused heat is not easy to distribute during penetrating, so as to influence the stability of non-equilibrium materials.The thickness of target is excessive, then
Heat caused by Ar+ sputterings is difficult to be transmitted on negative electrode in the thickness direction of target on the target surface, so that target
Surface temperature rises, and destroys its stability.
3rd, the negative electrode of sputter chamber needs to be cooled down with the recirculated water of low temperature, to control the temperature of negative electrode, to improve target
The heat conduction efficiency of material thickness direction, play preferable thermolysis.Preferably, the temperature of cooling water should be controlled≤10
℃。
The dynamic conditions of substrate and film controls：Work as GeSe4When being splashed to formation film in substrate, GeSe4At film
In quasi-stable state, it is necessary to create favourable dynamic conditions, make the GeSe in substrate4Stable Ge can be kept inside film
With Se atomic ratio, so as to keep the physical property of its material.Temperature control can use following measure.
1st, substrate carries out active cooling with recirculated water, the temperature of film surface is held in low-temperature condition, recirculated cooling water
Temperature should control at≤10 DEG C；
2nd, using in-situ sputtering method, the GeSe formed in substrate4Film surface sputters one layer of stable pottery again
Porcelain thin-film material, such as ZnSe, SiO2、Al2O3Etc..GeSe4The ceramic membrane of film surface can be by GeSe4The height of the inside is waved
Hair property Se atoms suppress in GeSe4Inside film, prevent that Se atoms from vaporing away and the decomposition of nonequilibrium state compound.
Embodiment 3
Present embodiments provide a kind of nonequilibrium state compound GeSe4, it is made by the following method：
First, by Se and Ge according to weight ratio 51:10 ratio is put into a high-purity quartz ampoule, is made in quartz ampoule
Vacuum reaches 5.0 × 10-3Pa, it is then that quartz ampoule is closed.
Secondly, closed quartz ampoule is put into resistance-heated furnace and heated, Ge and Se mixture is reached full liquid, with
Just fully react.Firing rate in resistance-heated furnace is 180 DEG C/h, and Ge and Se temperature are heated to 930 DEG C.
Kept for 3.0 hours at 930 DEG C, the quartz ampoule is placed on a device that mechanical can be rocked by insulation simultaneously, with 1.0Hz's
Frequency is rocked, and Ge and Se elements is equably reacted.
Again, after fully being reacted 3.0 hours under conditions of closed and high temperature, the power supply of resistance-heated furnace is cut off, will
Closed quartz ampoule takes out out of resistance-heated furnace body；Then the air of room temperature is blown to quartz ampoule periphery, is passed by cross-ventilation
Heat completes fast cooling.The speed to cool in the present embodiment can reach 10 DEG C/min, when temperature drops to the process of room temperature
In, that from the taking-up of quartzy tubular container is exactly stable nonequilibrium state GeSe4。
Embodiment 4
Present embodiments provide a kind of nonequilibrium state chalcogenide GeSe4 films, the nonequilibrium state chalcogenide
GeSe4 films are made by following methods.
The first step, the preparation method provided according to embodiment 3 make nonequilibrium state GeSe4。
Second step, by nonequilibrium state GeSe obtained above4In the vapor tight tank for placing applying argon gas, then vapor tight tank is put
Powder is made in planetary ball mill.The average-size of powder is preferably controlled in 100 microns.
3rd step, manufactured powder is positioned in the graphite jig of high-purity, graphite jig is then put into hot press
Cavity in, vacuum in the cavity of hot press is 3.0 × 10-3Pa.The temperature in the cavity of hot press is controlled to rise to 310
DEG C, pressure rises to 500 tons, and maintains the condition 3.0 hours.After maintaining reaction in 3.0 hours, heating power supply and high pressure shape are released
State, the nitrogen of room temperature is blown the graphite jig in cavity, make the powder after hot-pressing processing with average 120 DEG C of speed per hour
Degree cooling is until room temperature.Bulk is taken out from graphite jig, then a diameter of 125mm is processed into by grinding machine, thickness is
4.2mm sputtering target material.
4th step, GeSe4Target is installed to plasma chamber and sputtered, so as to form nonequilibrium state in substrate
GeSe4Film, the film can finally make memory body chip key OTS films.In sputter procedure, made on cathode electrode
Power is 140W, and the electrode and substrate of sputter chamber are both provided with the circulating cooling water management of active, and coolant water temperature is set
At 10 DEG C.
Embodiment 5
Present embodiments provide a kind of nonequilibrium state compound GeS4, it is made by the following method：
First, by S and Ge according to weight ratio 49:25 ratio is put into a high-purity quartz ampoule, is made in quartz ampoule
Vacuum reaches 2.0 × 10-3Pa, it is then that quartz ampoule is closed.
Secondly, closed quartz ampoule is put into resistance-heated furnace and heated, firing rate is 180 DEG C/h, reaches temperature
To 700 DEG C, Ge and S mixture is set to reach full liquid.Kept for 3.4 hours at 700 DEG C, insulation simultaneously places the quartz ampoule
On the device that one mechanical can rock, rocked with 0.5Hz frequency, Ge and S elements is equably reacted.
Again, after fully being reacted 3.4 hours under conditions of closed and high temperature, the power supply of resistance-heated furnace is cut off, will
Closed quartz ampoule takes out out of resistance-heated furnace body；Then the air of room temperature is blown to quartz ampoule periphery, is passed by cross-ventilation
Heat completes fast cooling.The average speed to cool in the present embodiment can reach 10 DEG C/min, when temperature drops to the mistake of room temperature
Cheng Zhong, that from the taking-up of quartzy tubular container is exactly stable nonequilibrium state GeS4。
Embodiment 6
Present embodiments provide a kind of nonequilibrium state GeS4Film, it is made by the following method：
The first step, the preparation method provided according to embodiment 5 make nonequilibrium state GeS4。
Second step, by nonequilibrium state GeS obtained above4In the vapor tight tank for placing applying argon gas, then vapor tight tank is put
Powder is made in planetary ball mill, and the average-size of powder is preferably controlled in 75 microns.
3rd step, manufactured powder is positioned in the graphite jig of high-purity, graphite jig is then put into hot press
Cavity in, vacuum in the cavity of hot press is 2.5 × 10-3Pa.The temperature in the cavity of hot press is controlled to rise to 340
DEG C, pressure rises to 500 tons, and maintains the condition 3.0 hours.After maintaining reaction in 3.0 hours, heating power supply and high pressure shape are released
State, the nitrogen of room temperature is blown the graphite jig in cavity, make the powder after hot-pressing processing with average 180 DEG C of speed per hour
Degree is cooled to room temperature.Bulk is taken out from graphite jig, then a diameter of 125mm, thickness 4.2mm are processed into by grinding machine
Sputtering target material.
4th step, GeS4Target is installed to plasma chamber and sputtered, so as to form nonequilibrium state in substrate
GeS4Film, the film can finally make memory body chip key OTS films.In sputter procedure, made on cathode electrode
Power is 150W, and the electrode and substrate of sputter chamber are both provided with the circulating cooling water management of active, and coolant water temperature is set
At 10 DEG C.
Embodiment 7
Present embodiments provide a kind of nonequilibrium state compound GeS4, nonequilibrium state compound GeS4By the following method
It is made：
First, by S and Ge according to weight ratio 21:10 ratio is put into a high-purity quartz ampoule, is made in quartz ampoule
Vacuum reaches 3.0 × 10-3Pa, it is then that quartz ampoule is closed.
Secondly, closed quartz ampoule is put into resistance-heated furnace and heated, firing rate is 180 DEG C/h, reaches temperature
To 770 DEG C, Ge and S mixture is set to reach full liquid.Kept for 3.0 hours at 770 DEG C, insulation simultaneously places the quartz ampoule
On the device that one mechanical can rock, rocked with 1.0Hz frequency, Ge and S elements is equably reacted.
Again, after fully being reacted 3.0 hours under conditions of closed and high temperature, the power supply of resistance-heated furnace is cut off, will
Closed quartz ampoule takes out out of resistance-heated furnace body；Then the air of room temperature is blown to quartz ampoule periphery, is passed by cross-ventilation
Heat completes fast cooling.The speed averagely to cool in the present embodiment can reach 10 DEG C/min, when temperature drops to the mistake of room temperature
Cheng Zhong, that from the taking-up of quartzy tubular container is exactly stable nonequilibrium state GeS4。
Embodiment 8
Present embodiments provide a kind of nonequilibrium state GeS4Film, it is made by the following method：
The first step, the preparation method provided according to embodiment 7 make nonequilibrium state GeS4。
Second step, by nonequilibrium state GeS obtained above4In the vapor tight tank for placing applying argon gas, then vapor tight tank is put
Powder is made in planetary ball mill, and the average-size of powder is preferably controlled in 110 microns.
3rd step, manufactured powder is positioned in the graphite jig of high-purity, graphite jig is then put into hot press
Cavity in, vacuum in the cavity of hot press is 3.0 × 10-3Pa.The temperature in the cavity of hot press is controlled to rise to 390
DEG C, pressure rises to 500 tons, and maintains the condition 2.9 hours.After maintaining reaction in 2.9 hours, heating power supply and high pressure shape are released
State, the nitrogen of room temperature is blown the graphite jig in cavity, make the powder after hot-pressing processing with average 120 DEG C of speed per hour
Degree is cooled to room temperature.Bulk is taken out from graphite jig, then a diameter of 125mm, thickness 4.5mm are processed into by grinding machine
Sputtering target material.
4th step, GeS4Target is installed to plasma chamber and sputtered, so as to form nonequilibrium state in substrate
GeS4Film, the film can finally make memory body chip key OTS films.In sputter procedure, made on cathode electrode
Power is 130W, and the electrode and substrate of sputter chamber are both provided with the circulating cooling water management of active, and coolant water temperature is set
At 10 DEG C.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (7)
- It is XY that 1. one kind, which is used to prepare chemical molecular formula,4Nonequilibrium state chalcogenide method, the nonequilibrium state chalcogenide Compound includes GeSe4、GeS4、CuS4、CuSe4、GeTe4、ZnSe4, Y is chalcogen, it is characterised in that methods described include with Lower step：1) it is X element and Y element is higher than the desired proportions required by molecular formula relative to the part by weight of X element according to Y element 10%~20% weight ratio is mixed, and is then placed them into vacuum equipment, wherein the vacuum in the vacuum equipment Spend for 1.0 × 10-3Pa~5.0 × 10-3Pa；2) vacuum equipment is heated, so that X element and Y element become molten state, X element is existed with Y element Reacted under constant temperature；3) air of room temperature after completion of the reaction, is blown the vacuum equipment periphery, mixes the liquid that X element and Y element form Compound is quickly cooled down with 10 DEG C~15 DEG C/min of rate of temperature fall, and the liquefied mixture is cooled to room temperature, steady to obtain Fixed nonequilibrium state chalcogenide.
- 2. according to the method for claim 1, it is characterised in that the mixing being made up of in the step 2) X element and Y element The temperature of thing is 700 DEG C~1200 DEG C, and heating rate is 150 DEG C/h~200 DEG C/h, and the isothermal reaction time is 3~4 small When.
- 3. method according to claim 1 or 2, it is characterised in that the step 2) is further comprising the steps of：While X element is reacted with Y element under constant temperature, the vacuum equipment is vibrated, vibration frequency is 0.5~1Hz.
- A kind of 4. method for making nonequilibrium state chalcogenide film, it is characterised in that comprise the following steps：A) by making stable nonequilibrium state chalcogenide according to the method any one of claim 1-3；B the nonequilibrium state chalcogenide) is handled by the method for powder metallurgy, to obtain sputtering target material；C) by target described in plasma sputtering, so as to form stable nonequilibrium state chalcogenide film in substrate.
- It is 5. according to the method for claim 4, it is characterised in that step B) further comprising the steps of：Powder is made in the nonequilibrium state chalcogenide of the stabilization of preparation；It is 1 × 10 in vacuum-3Pa~3 × 10-3Pa, temperature Spend for 280 DEG C~400 DEG C, pressure sinters the powder 2.8~3 hours under conditions of being 400~600 tons, and cooling is made highly dense Spend material；Target is made in obtained high density material.
- 6. according to the method for claim 5, it is characterised in that rate of temperature fall during cooling is 80~130 DEG C/h.
- 7. according to the method for claim 6, it is characterised in that step C) in the plasma sputtering condition be：Institute The temperature for stating target material surface is not higher than 100 DEG C, and the negative electrode and substrate in sputter chamber are not higher than 10 DEG C of recirculated water cooling with temperature But, the Sputtering power density of negative electrode is not higher than 1.25W/cm2, the thickness of target is less than 5 millimeters.
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| KR102295524B1 (en) * | 2017-03-27 | 2021-08-30 | 삼성전자 주식회사 | Memory device |
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