CN105489758B - Si/Sb class superlattices phase change film materials for phase transition storage and preparation method thereof - Google Patents

Si/Sb class superlattices phase change film materials for phase transition storage and preparation method thereof Download PDF

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CN105489758B
CN105489758B CN201510889657.2A CN201510889657A CN105489758B CN 105489758 B CN105489758 B CN 105489758B CN 201510889657 A CN201510889657 A CN 201510889657A CN 105489758 B CN105489758 B CN 105489758B
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sputtering
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CN105489758A (en
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朱小芹
胡益丰
邹华
袁丽
吴卫华
郑龙
张建豪
吴世臣
眭永兴
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Jiangsu University of Technology
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801Constructional details of multistable switching devices
    • H10N70/881Switching materials
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011Manufacture or treatment of multistable switching devices
    • H10N70/021Formation of switching materials, e.g. deposition of layers
    • H10N70/026Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20Multistable switching devices, e.g. memristors

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  • Physical Vapour Deposition (AREA)
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Abstract

The invention discloses a kind of Si/Sb class superlattices phase change film materials for phase transition storage, Si/Sb class superlattices phase change film material is multi-layer film structure, and Si film layers and Sb film layers are alternately arranged in multi-layer film structure.The RESET voltage of the Si/Sb class superlattices phase change film materials of the present invention is than the Ge under identical voltage impulses2Sb2Te5The RESET voltage low more than 47% of film, illustrating the Si/Sb class superlattices phase change film material of the present invention has lower power consumption.

Description

For the Si/Sb class superlattices phase change film materials of phase transition storage and its preparation Method
Technical field
The present invention relates to the phase change film material of microelectronics technology, and in particular to one kind is used for high speed, low-power consumption phase Si/Sb class superlattices phase change film materials of transition storage and preparation method thereof.
Background technology
At present, the novel memory devices with application potential are mainly magnetic memory(MRAM), ferroelectric memory (FeRAM), resistance-variable storing device(RRAM)And phase transition storage(PCRAM).Wherein phase transition storage is as non-volatile memories Device, has high speed, high density, high data retention, high circulation service life(>1013It is secondary), low-power consumption, preparation process it is simple and with Many advantages, such as existing integrated circuit technology is mutually compatible, especially scaling performance is good(Can be with micro to 5 nm technology nodes), have May the dynamic memory of substitution currently on the market(DRAM), flash memory(Flash)And mechanical hard disk(HDD)Deng becoming next The general-purpose storage in generation.The principle of PCRAM is come real using chalcogenide compound in the huge resistance difference of crystalline state and amorphous state Existing data storage, has high electrical resistance when phase-change material is in amorphous state, in crystalline state with compared with low resistance, the electricity between binary states Resistance difference reaches more than 2 orders of magnitude.Pass through the Joule heat of current induced, it is possible to achieve phase-change material is between two Resistance states Fast transition.PCRAM is considered most possibly to substitute at present with its big advantage by International Semiconductor Industry Association Flash memory and as future memory main product and at first as commercial product nonvolatile memory of future generation.
Phase-change storage material is the core of PCRAM, its performance directly determines every technical performance of PCRAM.Phase change memory The service speed of device is primarily limited to the crystallization process of film, therefore the phase velocity for accelerating film could improve phase transition storage Service speed.
Current most widely used phase-change storage material is Ge2Sb2Te5 (GST), it has preferable comprehensive performance;But Its relatively low crystallization temperature and poor heat endurance make it that the data retention of GST is unsatisfactory, exist many to be improved With the place of raising(Loke, D. etc., Science, 2012,336(6088): 1566).Such as Ge2Sb2Te5The crystalline substance of film Change temperature and there was only 160 DEG C or so, be only capable of under 85 DEG C of environment temperature keeping data 10 years, secondly, Ge2Sb2Te5Film with Crystallization Mechanism based on forming core make it that its phase velocity is slower, can not meet that following high speed, the storage of the information in big data epoch will Ask.
In recent years, class superlattices phase-change material is given more sustained attention, with traditional individual layer Ge2Sb2Te5Phase-change material is compared, Class superlattice structure has relatively low thermal conductivity, it is possible to reduce the heat in heating process scatters and disappears, so as to improve the efficiency of heating surface.Hair Bright content
The technical problems to be solved by the invention are to provide a kind of for high speed, the Si/Sb classes of low power consumption phase changing memory Superlattices phase change film material and preparation method thereof.
The technical solution for realizing the object of the invention is a kind of Si/Sb class superlattices phase-change thin film materials for phase transition storage Material, Si/Sb class superlattices phase change film material be multi-layer film structure, and Si film layers and Sb film layers replace in multi-layer film structure Arrangement.
The membrane structure of Si/Sb class superlattices phase change film materials is with general formula [Si (a)/Sb (b)]xRepresent, wherein a is single The thickness of layer Si film layers, 1nm≤a≤22nm;B be individual layer Sb film layers thickness, 1nm≤b≤5nm;X for Si film layers and The alternate cycle number of Sb film layers, x are positive integer.
As preference, 40nm≤(a+b)×x≤65nm.
A kind of preparation method of the Si/Sb class superlattices phase change film materials as described above for phase transition storage, bag Include following steps:
1. the preparation of substrate, it is stand-by to clean drying by substrate.
2. the preparation of magnetron sputtering, by step, 1. clean substrate to be sputtered is placed on base, using Si and Sb as Sputtering target material is separately mounted in magnetron RF sputtering system target, and the sputtering chamber of magnetron sputtering coating system is vacuumized, Sputter gas is used as using high-purity argon gas.
3. magnetron sputtering is prepared [Si (a)/Sb (b)]xMulti-layer compound film, cleans Si targets and Sb target material surfaces first, After cleaning, by SiO to be sputtered2/Si(100)Substrate rotates to Si target position;Open the radio-frequency power supply on Si target position, sputtering After obtain Si film layers;After the completion of the sputtering of Si film layers, the DC power supply applied is closed on Si target position, will have been sputtered The substrate of Si film layers rotates to Sb target position, opens the radio-frequency power supply on Sb target position, Sb film layers are obtained after sputtering;Repeat Above-mentioned sputtering Si layers and Sb layers of operation to the film thickness needed, sputtering end obtains Si/Sb class superlattices phase-change thin film materials Material.
3. middle Si layers of sputter rate is 15s/nm to above-mentioned steps, and Sb layers of sputter rate are 3s/nm.
Percent by volume >=99.999%, Ar throughput of above-mentioned steps 2. middle high-purity argon gas is 25~35SCCM, and argon gas splashes Pressure of emanating is 0.15Pa~0.4Pa.
The present invention has positive effect:(1)The Si/Sb class superlattices phase change film material of the present invention utilizes class superlattices The clamping effect of more bed boundarys in structure, reduces crystallite dimension, so as to shorten crystallization time, suppresses crystallization, is improving thermostabilization Accelerate phase velocity while property.
(2)Stereomutation of the Si/Sb class superlattices phase change film materials of the present invention in phase transition process is smaller, Ke Yibao Effective good contact of phase change layer and electrode material is demonstrate,proved, so as to improve the reliability of PCRAM devices.
(3)The Si/Sb class superlattices phase change film materials of the present invention by Ge layer of magnetron sputtering alternating deposit and Sb layers, Nanometer scale is combined.During preparation, the thickness of each Ge layers and Sb layers are controlled by controlling sputtering time and sputter rate, respectively The thickness control of layer is accurate.
(4)The RESET voltage of the Si/Sb class superlattices phase change film materials of the present invention is than under identical voltage impulses Ge2Sb2Te5The RESET voltage low more than 47% of film, illustrating the Si/Sb class superlattices phase change film material of the present invention has more Low power consumption.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention 1 to the Si/Sb class superlattices phase change film materials of embodiment 6 and the original position of comparative example 1 The relation curve of resistance and temperature, the Temperature of abscissa is temperature in figure, and the Resistance of ordinate is resistance;
Fig. 2 is by the Si/Sb class superlattices phase change film materials of the embodiment of the present invention 2 and tradition Ge2Sb2Te5Thin-film material After PCRAM device cells are made, test voltage pulse effect under resistance with voltage variation relation;Abscissa in figure Voltage is voltage, and the Resistance of ordinate is resistance.
Embodiment
(Embodiment 1)
The Si/Sb class superlattices phase change film material for phase transition storage of the present embodiment is multi-layer film structure, thickness For 40~65nm;Si film layers and Sb film layers are alternately arranged in multi-layer film structure, i.e., in Si/Sb class superlattices phase-change thin film materials In material, repeat to be alternately arranged according to the order of Si film layer-Sb film layer-Si film layer-Sb film layers ....By one layer of Si film Layer and one layer of Sb film layer are as an alternate cycle, and the Si thin film layers of the latter alternate cycle are in previous alternate cycle Sb film layers above.
Wherein the thickness of individual layer Si film layers is 1~22nm, and the thickness of individual layer Sb film layers is 1~5nm.In Si film layers Si contents more than 99.999%, Sb contents more than 99.999% in Sb film layers.
The membrane structure of above-mentioned Si/Sb classes superlattices phase change film material is with general formula [Si (a)/Sb (b)]xRepresent, wherein a For the thickness of individual layer Si film layers, 1nm≤a≤22nm;B be individual layer Sb film layers thickness, 1nm≤b≤5nm;X is Si films The alternate cycle number of layer and Sb film layers, one layer of Si film layer and one layer of Sb film layer are one group in other words, and thin-film material is by x groups Si film layers and Sb the film layers composition of individual layer;X is positive integer, 40nm≤(a+b)×x≤65nm.
The membrane structure of the Si/Sb class superlattices phase change film materials of the present embodiment is [Si (1nm)/Sb (5nm)]8, i.e., it is every The thickness of one layer of Si film layer is 1nm, and the thickness of each layer of Sb film layer is the alternating week of 5nm, Si film layers and Sb film layers Issue is that the thickness of 8, Si/Sb class superlattices phase change film materials is 48nm.
The Si/Sb class superlattices phase change film materials of the present embodiment are made using magnetron sputtering method;Specific preparation method bag Include following steps:
1. the preparation of substrate.Choose the SiO that size is 5mm × 5mm2/Si(100)Substrate, first will in supersonic cleaning machine Substrate is in acetone(Purity is more than 99%)It is middle to be cleaned by ultrasonic 3~5 minutes, wash complete taking-up deionized water rinsing;Then in ultrasound By substrate in ethanol in cleaning machine(Purity is more than 99%)It is middle to be cleaned by ultrasonic 3~5 minutes, complete taking-up deionized water rinsing is washed, High-purity N is used after rinsing well2Dry up surface and the back side;Substrate after drying, which is sent into baking oven, dries steam, the substrate after drying Stand-by, wherein oven temperature is arranged to 120 DEG C, drying time 20 minutes.
2. the preparation of magnetron sputtering.
In magnetron sputtering coating system(JGP-450 types)In, 1. SiO to be sputtered that step is prepared2/Si(100)Base Piece is placed on base, by Si(Atomic percent 99.999%)And Sb(Atomic percent 99.999%)Distinguish as sputtering target material Installed in magnetic control radio frequency(RF)In sputtering target, and the sputtering chamber of magnetron sputtering coating system vacuumize until in chamber Vacuum reaches 1 × 10-4 Pa。
Use high-purity argon gas(Percent by volume reaches 99.999%)As sputter gas, set Ar throughputs as 25~ 35SCCM(It is 30SCCM in the present embodiment), and sputtering pressure is adjusted to 0.15~0.4Pa(It is 0.4Pa in the present embodiment).
The sputtering power of radio-frequency power supply is set as 25W~35W(It is 30W in the present embodiment).
3. magnetron sputtering is prepared [Si (a)/Sb (b)]xMulti-layer compound film.
Si targets and Sb target material surfaces are cleaned first.Space base support is rotated into Si target position, opens the direct current on Si target position Source, sets sputtering time 100s, starts to sputter Si target material surfaces, cleans Si target material surfaces;Si target material surfaces have cleaned Bi Hou, closes on Si target position the radio-frequency power supply applied, and space base support is rotated to Sb target position, opens the radio-frequency power supply on Sb target position, Sputtering time 100s is set, starts to sputter Sb target material surfaces, cleans Sb target material surfaces, the cleaning of Sb target material surfaces finishes Afterwards, the DC power supply that applies is closed on Sb target position, by SiO to be sputtered2/Si(100)Substrate rotates to Si target position.
Then the Si film layers of first alternate cycle of sputtering are started:The radio-frequency power supply on Si target position is opened, sets Si layers Sputter rate is 15s/nm, sputtering time 15s, and the Si film layers of 1nm thickness are obtained after sputtering.
After the completion of the sputtering of Si film layers, the radio-frequency power supply applied is closed on Si target position, Si film layers will have been sputtered Substrate rotates to Sb target position, opens the radio-frequency power supply on Sb target position, sets Sb layers of sputter rate as 3s/nm, sputtering time 15s, The Sb film layers of 5nm thickness are obtained after sputtering.
Above-mentioned sputtering Si layers and Sb layers are repeated on the substrate for having sputtered one layer of Si film layer and one layer of Sb film layer Operation 7 times, it is [Si (1)/Sb (5)] to obtain the membrane structure with 8 alternate cycles8Si/Sb class superlattices phase-change thin films Material.
In addition, on the premise of gross thickness is fixed, for the film of a certain definite periodicity, by controlling Si and Sb targets Sputtering time adjust the thickness of Si and Sb single thin films in the film cycle so that the Si/Sb classes of structure surpass crystalline substance needed for being formed Lattice phase change film material.
(Embodiment 2)
The membrane structure of the Si/Sb class superlattices phase change film materials for phase transition storage of the present embodiment is [Si (11nm)/Sb(5nm)]3, i.e., the thickness of each layer Si film layer is 11nm, and the thickness of each layer of Sb film layer is 5nm, Si layers Alternate cycle number with Sb layers is that the thickness of 3, Si/Sb class superlattices phase change film materials is 48nm.
Remaining is same as Example 1 for preparation method, and difference is:3. magnetron sputtering prepares [Si (a)/Sb to step (b)]xDuring multi-layer compound film, the sputtering time of each layer of Si film layer is 165s.Si layers and Sb layers of alternating sputtering 3 times.
(Embodiment 3)
The membrane structure of the Si/Sb class superlattices phase change film materials for phase transition storage of the present embodiment is [Si (10nm)/Sb(2nm)]4, i.e., the thickness of each layer Si film layer is 10nm, and the thickness of each layer of Sb film layer is 2nm, Si layers Alternate cycle number with Sb layers is that the thickness of 4, Si/Sb class superlattices phase change film materials is 48nm.
Remaining is same as Example 1 for preparation method, and difference is:3. magnetron sputtering prepares [Si (a)/Sb to step (b)]xDuring multi-layer compound film, the sputtering time of each layer of Si film layer is 150s, and the sputtering time of each layer of Sb film layer is 6s.Si layers and Sb layers repeat alternating sputtering 4 times.
(Embodiment 4)
The membrane structure of the SiSb class superlattices phase change film materials for phase transition storage of the present embodiment is [Si (18nm)/Sb(2nm)]3, i.e., each layer Si layers of thickness is 18nm, and each layer Sb layers of thickness is 2nm, Si layers and Sb layers Alternate cycle number is that the thickness of 3, Si/Sb class superlattices phase change film materials is 60nm.
Remaining is same as Example 1 for preparation method, and difference is:3. magnetron sputtering prepares [Si (a)/Sb to step (b)]xDuring multi-layer compound film, the sputtering time of each layer of Si film layer is 270s, and each layer Sb layers of sputtering time is 6s. Si layers and Sb layers repeat alternating sputtering 3 times.
(Embodiment 5)
The membrane structure of the Si/Sb class superlattices phase change film materials for phase transition storage of the present embodiment is [Si (22nm)/Sb(2nm)]2, i.e., each layer Si layers of thickness is 22nm, and each layer Sb layers of thickness is 2nm, Si layers and Sb layers Alternate cycle number is that the thickness of 2, Si/Sb class superlattices phase change film materials is 44nm.
Remaining is same as Example 1 for preparation method, and difference is:3. magnetron sputtering prepares [Si (a)/Sb to step (b)]xDuring multi-layer compound film, the sputtering time of each layer of Si film layer is 330s, and each layer Sb layers of sputtering time is 6s. Si layers and Sb layers repeat alternating sputtering 2 times.
(Embodiment 6)
The membrane structure of the Si/Sb class superlattices phase change film materials for phase transition storage of the present embodiment is [Si (18nm)/Sb(1nm)]3, i.e., each layer Si layers of thickness is 18nm, and each layer Sb layers of thickness is 1nm, Si layers and Sb layers Alternate cycle number is that the thickness of 3, Si/Sb class superlattices phase change film materials is 57nm.
Remaining is same as Example 1 for preparation method, and difference is:3. magnetron sputtering prepares [Si (a)/Sb to step (b)]xDuring multi-layer compound film, the sputtering time of each layer of Si film layer is 270s, and the sputtering time of each layer of Sb film layer is 3s.Si layers and Sb layers repeat alternating sputtering 3 times.
(Comparative example 1)
Prepared by this comparative example is individual layer Sb phase change film materials, thickness 50nm.According to the method for embodiment 1, Sb is set Sputter rate is 3s/nm, sputtering time 150s, and the individual layer Sb phase change film materials of 50nm thickness are obtained after sputtering.
(Comparative example 2)
That prepared by this comparative example is Ge2Sb2Te5Phase change film material, thickness 50nm.According to the method for embodiment 1, selection Ge2Sb2Te5Alloy obtains Ge as sputtering target material, sputtering end2Sb2Te5Phase change film material.
(Experimental example 1)
In order to understand the performance of the Si/Sb class superlattices phase change film materials of the present invention, embodiment 1 to embodiment 6 is made Thin-film material made from the thin-film material and comparative example 1 obtained is tested, and obtains the In-situ resistance and temperature of each phase change film material The relation curve of degree.
See Fig. 1, the individual layer Sb films of comparative example 1 do not have resistance switching performance in heating process, show Sb materials Heat endurance is poor, just there occurs crystallization in deposition process, can not meet the application demand of PCRAM.
For the Si/Sb class superlattices phase change film materials of the present invention, with [Si (a)/Sb (b)]xClass superlattices phase transformation The increase of Si layers of relative thickness in film, the crystallization temperature of phase-change thin film gradually step up, and the crystallization temperature of higher means phase transformation The more preferable amorphous heat endurance of film.Secondly, with the increase of Si layers of relative thickness, the amorphous state of film and the resistance of crystalline state Increase, the resistance of bigger helps to improve the efficiency of heating process, so as to reduce operation power consumption.
(Experimental example 2)
This experimental example uses [Si (22nm)/Sb (2nm)] of embodiment 5 according to existing method2Class superlattices phase-change thin film The Ge of material and comparative example 22Sb2Te5Phase change film material is prepared for PCRAM device cells respectively, and tests its R-V curve, As shown in Figure 2.
Low-resistance operation is transformed into from high resistance and is known as SET processes, and is known as from low resistance to high-resistance process RESET operation.Since the switching current of RESET processes in PCRAM is larger, the mainly RESET electricity of evaluation PCRAM power consumptions Flow size.
See Fig. 2, under the effect of the voltage pulse of 10ns, 20ns and 200ns wide, [Si (22nm)/Sb (2nm)]2With Ge2Sb2Te5Device realize SET and RESET invertible operations.[Si(22nm)/Sb(2nm)]2Film is in 10ns wide, 20ns RESET voltage difference 2.30V and 1.91V under Width funtion impulse action, RESET voltage increase and subtract with Voltage Pulse Width It is small, if Voltage Pulse Width is increased to 200ns, [Si (22nm)/Sb (2nm)]2RESET voltage will be lower, and 200ns Under wide voltage pulse effect, Ge2Sb2Te5The RESET voltage of film is 3.62V, shows [the Si (22nm)/Sb of the present invention (2nm)]2Superlattice film and Ge2Sb2Te5Film, which is compared, has relatively low power consumption.

Claims (5)

  1. A kind of 1. Si/Sb class superlattices phase change film materials for phase transition storage, it is characterised in that:Si/Sb class superlattices Phase change film material is multi-layer film structure, and Si film layers and Sb film layers are alternately arranged in multi-layer film structure;
    The membrane structure of Si/Sb class superlattices phase change film materials is with general formula [Si (a)/Sb (b)]xRepresent, wherein a is thin for individual layer Si The thickness of film layer, 10nm≤a≤22nm;B be individual layer Sb film layers thickness, 1nm≤b≤5nm;X is thin for Si film layers and Sb The alternate cycle number of film layer, x are positive integer.
  2. 2. the Si/Sb class superlattices phase change film materials according to claim 1 for phase transition storage, its feature exists In:40nm≤(a+b)*x≤65nm.
  3. A kind of 3. preparation side of the Si/Sb class superlattices phase change film materials as claimed in claim 1 for phase transition storage Method, it is characterised in that comprise the following steps:
    1. the preparation of substrate, it is stand-by to clean drying by substrate;
    2. the preparation of magnetron sputtering, 1. substrate to be sputtered that step is cleaned is placed on base, using Si and Sb as sputtering Target is separately mounted in magnetron RF sputtering system target, and the sputtering chamber of magnetron sputtering coating system is vacuumized, and is used High-purity argon gas is as sputter gas;
    3. magnetron sputtering is prepared [Si (a)/Sb (b)]xMulti-layer compound film, cleans Si targets and Sb target material surfaces, cleaning first After, by SiO to be sputtered2/Si(100)Substrate rotates to Si target position;The radio-frequency power supply on Si target position is opened, sputtering terminates After obtain Si film layers;After the completion of the sputtering of Si film layers, the DC power supply applied is closed on Si target position, it is thin by Si has been sputtered The substrate of film layer rotates to Sb target position, opens the radio-frequency power supply on Sb target position, Sb film layers are obtained after sputtering;Repeat above-mentioned The operation of Si layers and Sb layers of sputtering to the film thickness needed, sputtering end obtains Si/Sb class superlattices phase change film materials.
  4. 4. the preparation method of the Si/Sb class superlattices phase change film materials according to claim 3 for phase transition storage, It is characterized in that:3. middle Si layers of sputter rate is 15s/nm to step, and Sb layers of sputter rate are 3s/nm.
  5. 5. the preparation method of the Si/Sb class superlattices phase change film materials according to claim 3 for phase transition storage, It is characterized in that:Percent by volume >=99.999%, Ar throughput of step 2. middle high-purity argon gas is 25~35SCCM, and argon gas splashes Pressure of emanating is 0.15Pa~0.4Pa.
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