CN107313023A - A kind of preparation method of Er ions molybdenum disulfide film - Google Patents

A kind of preparation method of Er ions molybdenum disulfide film Download PDF

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CN107313023A
CN107313023A CN201710421009.3A CN201710421009A CN107313023A CN 107313023 A CN107313023 A CN 107313023A CN 201710421009 A CN201710421009 A CN 201710421009A CN 107313023 A CN107313023 A CN 107313023A
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temperature
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molybdenum disulfide
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carrier gas
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CN107313023B (en
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蒲红斌
杨勇
张珊
邸君杰
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Xian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material

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  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A kind of preparation method of Er ions molybdenum disulfide film of disclosure of the invention, comprises the following steps：Step 1, sulphur powder is placed in a warm area；Molybdenum trioxide powder and erbium chloride powder are placed in two warm areas；Crucible surface is placed the substrate in, crucible is then placed on three-temperature-zone；It step 2, will be vacuumized in vacuum tube furnace, carrier gas led into vacuum tube furnace and is cleaned；The carrier gas is led in step 3, continuation, and two warm areas are heated into 150~350 DEG C, three-temperature-zone is heated into 150~350 DEG C；The thermograde of step 4, setting three-temperature-zone prevapourising and pre-nucleating is 150 DEG C~150 DEG C, obtains gaseous MoO3‑x, wherein 0<x≤1；Step 5, section：A warm area is heated to 130~220 DEG C, sulfur vapor is obtained；Two warm areas are heated to 800 DEG C~900 DEG C；Three-temperature-zone is heated to 700 DEG C~850 DEG C；Step 6, a warm area, two warm areas and three-temperature-zone be down to room temperature, obtain molybdenum disulfide film.The present invention realizes the control of molybdenum disulfide film pattern by controlling the thermograde between prevapourising temperature and preformation nuclear temperature.

Description

A kind of preparation method of Er ions molybdenum disulfide film
Technical field
The present invention relates to chemical vapor deposition preparing technical field, and in particular to a kind of system of Er ions molybdenum disulfide film Preparation Method.
Background technology
Two-dimensional layer material molybdenum disulfide is due to relying on faint van der waals force heap between Covalent bonding together, layer in face Stack, show many novel physical attributes.The research of luminescence generated by light attribute from individual layer to multilayer is to two-dimentional material Expect that there is very big latent space in application fields such as opto-electronic device, communications.But seen at present in all two-dimensional layer materials The luminescence generated by light and electroluminescent main emission peak observed is concentrated within the scope of visible near-infrared (NIR).Therefore, adjust The luminescence generated by light attribute of excimer, energy band and number of plies influence is particularly important.It is existing regulation luminescence generated by light main method be Prepare after molybdenum disulfide film using the progress chemical doping such as chlorauride, luminescence generated by light can only be adjusted in a small range.Rare earth The 4f electron orbits of erbium ion can realize ultraviolet absorption and transmitting near infrared region photon in occupation of abundant energy level. The luminous of rare earth ion has a high quantum generation efficiency, narrow bandwidth, long luminescence lifetime, high photostability and Stokes is inclined significantly Move.Particularly Er ions molybdenum disulfide can realize the transmitting at the luminescence generated by light peak of conversion and lower conversion near infrared region, and this is Material foundation has been established in the development of modern optoelectronic devices and optical communication.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Er ions molybdenum disulfide film, by control molybdenum trioxide and The prevapourising temperature and preformation nuclear temperature of erbium chloride, realize the preparation of large area Er ions molybdenum disulfide film.
The technical solution adopted in the present invention is, a kind of preparation method of Er ions molybdenum disulfide film, including following step Suddenly：
Step 1, using three-temperature-zone chemical gas-phase deposition system, sulphur powder is placed in a warm area；By molybdenum trioxide powder and chlorination Erbium powder is placed in two warm areas；Crucible bottom with cover is placed the substrate in, crucible is then placed on three-temperature-zone；
Step 2, will be vacuumized in quartz ampoule, into quartz ampoule in lead to carrier gas and cleaned；
Step 3, the first heating period：Continue to lead to the carrier gas, two warm areas are heated to 150~350 DEG C, keep 60~ 180min；Three-temperature-zone is heated to 150~350 DEG C, 60~180min is kept；
Step 4, the second heating period：Inflation makes quartzy intraductal pressure after atmospheric pressure, to adjust carrier gas flux, sets two temperature Area and three-temperature-zone temperature difference are 0~200 DEG C, and two area's temperature of heating keep 10~60min, obtain gaseous to 580~800 DEG C MoO3-x, wherein 0<x≤1；Three-temperature-zone is heated to 580~700 DEG C, 10~60min is kept；
Step 5, the 3rd heating period：A warm area is heated to 130~220 DEG C, 10~60min is kept, obtains sulfur vapor；
Step 6, the 4th heating period：Two warm areas are heated to 800 DEG C~950 DEG C, 10~60min is kept；By three-temperature-zone 750 DEG C~900 DEG C are heated to, 10~60min is kept；By the carrier gas by the sulfur vapor, erbium chloride steam and the gas The MoO of state3-xCarry to crucible reaction intracavitary, in substrate surface formation Er ions molybdenum disulfide film.
The features of the present invention is also resided in,
Sulphur powder and the mass ratio of molybdenum trioxide powder are in step 1：20：1~250:1；The matter of molybdenum trioxide powder and erbium chloride Measuring ratio is：1：1~6：1.
Substrate is silica, carborundum, silicon or sapphire in step 1.
Carrier gas is high pure nitrogen, argon gas, dilution hydrogen or high purity inert gas in step 2, and the flow velocity for being passed through carrier gas is 100 ~500ccm.
Flow rate of carrier gas is adjusted in step 5 to 10~80ccm.
The heating rate of the warm area of first heating period two and three-temperature-zone is 10~35 DEG C/min in step 3.
The heating rate of the warm area of second heating period two and three-temperature-zone is 15~50 DEG C/min in step 4.
The heating rate of the warm area of the 3rd heating period one is 20~40 DEG C/min in step 5.
The heating rate of the warm area of the 4th heating period two and three-temperature-zone is 5~50 DEG C/min in step 6.
A kind of beneficial effect of the preparation method of Er ions molybdenum disulfide film of the present invention is, in three-temperature-zone chemical vapor deposition Molybdenum source evaporating area introduces erbium chloride (ErCl in product system3·6H2O), by controlling the prevapourising temperature of molybdenum trioxide and erbium chloride With preformation nuclear temperature, the preparation of large area Er ions molybdenum disulfide film is realized；Because erbium chloride evaporating temperature is steamed than molybdenum source Send out temperature slightly higher, this provides condition for the two evaporation simultaneously, meanwhile, substrate is placed in quasi- closing crucible, effectively reduced The phase concentrations that molybdenum source and the evaporation of erbium source are produced, reduce Er ions nucleation density at initial stage, are that individual layer Er ions molybdenum disulfide is thin The large area deposition of film provides condition, and growth for large area Er ions molybdenum disulfide film provides necessary technology Support and experiment support.
Brief description of the drawings
Fig. 1 is the structural representation of the three-temperature-zone chemical gas-phase deposition system used in the present invention；
Fig. 2 is the optical microscope for the Er ions molybdenum disulfide film that the present invention is prepared；
Fig. 3 is the Raman figure for the Er ions molybdenum disulfide film that the present invention is prepared.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of preparation method of Er ions molybdenum disulfide film of the present invention, comprises the following steps：
Step 1, using three-temperature-zone chemical vapor deposition (CVD) system, sulphur powder is placed in a warm area；By molybdenum trioxide powder and Erbium chloride powder is placed in two warm areas；Crucible bottom with cover is placed the substrate in, crucible is then placed on three-temperature-zone；
Step 2, will be vacuumized in quartz ampoule, into quartz ampoule in lead to carrier gas and cleaned；
Step 3, the first heating period：Continue to lead to the carrier gas, two warm areas are heated to 150~350 DEG C, keep 60~ 180min；Three-temperature-zone is heated to 150~350 DEG C, 60~180min is kept；
Step 4, the second heating period：Inflation makes quartzy intraductal pressure after atmospheric pressure, to adjust carrier gas flux, sets two temperature Area and three-temperature-zone temperature difference are 0~200 DEG C, and two area's temperature of heating keep 10~60min, obtain gaseous to 580~800 DEG C MoO3-x, wherein 0<x≤1；Three-temperature-zone is heated to 580~700 DEG C, 10~60min is kept；
Step 5, the 3rd heating period：A warm area is heated to 130~220 DEG C, 10~60min is kept, obtains sulfur vapor；
Step 6, the 4th heating period：Two warm areas are heated to 800 DEG C~950 DEG C, 10~60min is kept；By three-temperature-zone 750 DEG C~900 DEG C are heated to, 10~60min is kept；By the carrier gas by the sulfur vapor, erbium chloride steam and the gas The MoO of state3-xCarry to crucible reaction intracavitary, in substrate surface formation Er ions molybdenum disulfide film.
Sulphur powder and the mass ratio of molybdenum trioxide powder are in step 1：20：1-250:1；The quality of molybdenum trioxide powder and erbium chloride Than for：1：1~6：1.
Substrate is silica, carborundum, silicon or sapphire in step 1.
Carrier gas is high pure nitrogen, argon gas, dilution hydrogen or high purity inert gas in step 2, and the flow velocity for being passed through carrier gas is 100 ~500ccm.
Flow rate of carrier gas is adjusted in step 5 to 10~80ccm.
The heating rate of the warm area of first heating period two and three-temperature-zone is 10~35 DEG C/min in step 3.
The heating rate of the warm area of second heating period two and three-temperature-zone is 15~50 DEG C/min in step 4.
The heating rate of the warm area of the 3rd heating period one is 20~40 DEG C/min in step 5.
The heating rate of the warm area of the 4th heating period two and three-temperature-zone is 5~50 DEG C/min in step 6.
The present invention prepares Er ions molybdenum disulfide with the three-temperature-zone CVD system shown in Fig. 1, wherein, a warm area and two, three temperature Area is separated, temperature independent control, two, three-temperature-zone temperature can realize coordinated signals, this is voltage input evaporating temperature, nucleation temperature respectively Degree and growth temperature provide condition.Substrate is placed on the bottom of quasi- closing crucible in the present invention in addition, and quasi- closing is meant that Referring to increases a lid on general crucible, allow inside crucible by crucible and the environment of the quasi- closing of crucible cover formation one, but There is the gap that gas can circulate between crucible cover and crucible, this avoids prevapourising, pre-nucleating stage and formed on substrate Too high nucleation density.On this condition, the principle for preparing Er ions molybdenum disulfide is：In the three-temperature-zone quartz ampoule shown in Fig. 1 Interior, sulphur source, molybdenum source, erbium source and crucible reprint specified location i.e. respectively, and sulphur powder is placed in into a warm area；By molybdenum trioxide powder and chlorine Change erbium powder and be placed in two warm areas；Crucible bottom with cover is placed the substrate in, crucible is then placed on three-temperature-zone, carrier gas is passed through.Two Temperature-raising region temperature raising to molybdenum source and erbium source prevapourising temperature, after temperature reach it is stable after, sulphur source is reached evaporating temperature, with sulphur source and Molybdenum source, the evaporation of erbium source, molybdenum sulphur erbium gas phase is transported to around crucible with carrier gas, and by accurate sealedly between crucible cover and crucible Gap reaches substrate surface, starts pre-nucleating；Then, two three-temperature-zones are warming up to molybdenum erbium source evaporating temperature and growth temperature respectively Degree, with the rise of temperature, reaction vulcanization reaction rate increase, erbium molybdenum sulphur phase concentrations increase, these gas phases are transported carrier gas It is transported to around quasi- closing crucible, is entered by the gap between crucible cover and crucible inside crucible, in quasi- enclosed environment condition Under, because molybdenum source is from limiting, Er ions molybdenum disulfide film is gradually formed in substrate surface.
The placement location of the part of three-temperature-zone system, reaction source and substrate is clearly illustrated in Fig. 1.
As can be seen from Figure 2 the Er ions molybdenum disulfide film prepared realizes large area uniform fold.
As can be seen from Figure 3 the raman characteristic peak of preparation-obtained Er ions molybdenum disulfide film be 384 ± 0.5cm-1With 404 ± 0.5cm-1, the difference between the two is 20 ± 0.5cm-1, Raman test result shows that prepared film is individual layer Film.
Embodiment 1
Step 1, using three-temperature-zone chemical vapor deposition (CVD) system shown in Fig. 1, it is 99.99% sulphur powder to take purity 100mg is placed in corundum boat, is placed in a warm area；Purity is 99.99% molybdenum trioxide powder and purity is 99.99% erbium chloride Powder is placed in corundum boat, is placed in two warm areas；Wherein molybdenum trioxide powder and erbium chloride silty amount are 5mg；Choose c-plane sapphire Or silica/silicon is cleaned as substrate, and to substrate；It is placed in quasi- closing crucible, then places crucible after drying In three-temperature-zone；
Step 2, the base vacuum in quartz ampoule is evacuated to below 1Pa using mechanical pump, into quartz ampoule in lead to inertia carry Gas：High pure nitrogen, the flow velocity for being passed through carrier gas is 100ccm, and flowing gas is cleaned for several times；
Step 3, the first heating period：Continue logical carrier gas, two warm areas are heated to 150 DEG C, three-temperature-zone is heated to 150 DEG C, keep 180min；The heating rate of two warm areas and three-temperature-zone is 5 DEG C/min；
Step 4, the second heating period：Inflation makes quartzy intraductal pressure reach after atmospheric pressure, adjusts carrier gas flux, sets two Warm area and three-temperature-zone temperature difference are 0 DEG C, and two area's temperature of heating keep 60min, obtain gaseous MoO to 580 DEG C3-x, wherein 0<x≤ 1；Three-temperature-zone is heated to 580 DEG C, 5min is kept；The heating rate of two warm areas and three-temperature-zone is 30 DEG C/min；
Step 5, the 3rd heating period：Second heating period temperature reaches after stabilization that one warm area of heating is kept to 130 DEG C 60min, obtains sulfur vapor；Heating rate is 20 DEG C/min；High pure nitrogen flow velocity is adjusted to 80ccm, by carrier gas by the sulphur Steam, erbium chloride steam and the gaseous MoO3-xCarry to crucible reaction intracavitary, in substrate surface pre-nucleating；
Step 6, the 4th heating period：Two warm areas are heated to 800 DEG C, 60min is kept, three-temperature-zone is heated to 750 DEG C, Keep 60min；Two temperature-raising region temperature raising speed are 22 DEG C/min, and the heating rate of three-temperature-zone is 17 DEG C/min；Will by the carrier gas The sulfur vapor, erbium chloride steam and the gaseous MoO3-xCarried with molybdenum disulfide gas phase to crucible reaction intracavitary, in substrate Surface forms Er ions molybdenum disulfide film.
Step 7, the vacuum tube furnace of a warm area is opened, room temperature is naturally cooling to, stops the supply of sulphur source, two, three-temperature-zone Less than 500 DEG C are cooled under carrier gas protection, two, three-temperature-zone stove is opened, starts to be naturally cooling to room temperature.
Embodiment 2
Step 1, using three-temperature-zone chemical vapor deposition (CVD) system shown in Fig. 1, it is 99.99% sulphur powder to take purity 300mg is placed in corundum boat, is placed in a warm area；Purity is 99.99% molybdenum trioxide powder and purity is 99.99% erbium chloride Powder is placed in corundum boat, is placed in two warm areas；Wherein molybdenum trioxide silty amount is 10mg, and erbium chloride silty amount is 5mg；Choose C Surface sapphire or silica/silicon are cleaned as substrate, and to substrate；It is placed in quasi- closing crucible, then will after drying Crucible is placed on three-temperature-zone；
Step 2, the base vacuum in quartz ampoule is evacuated to below 1Pa using mechanical pump, into quartz ampoule in lead to inertia carry Gas：High pure nitrogen, the flow velocity for being passed through carrier gas is 300ccm, and flowing gas is cleaned for several times；
Step 3, the first heating period：Continue logical carrier gas, two warm areas are heated to 200 DEG C, three-temperature-zone is heated to 200 DEG C, keep 100min；The heating rate of two warm areas and three-temperature-zone is 15 DEG C/min；
Step 4, the second heating period：Inflation makes quartzy intraductal pressure reach after atmospheric pressure, adjusts carrier gas flux, sets two Warm area and three-temperature-zone temperature difference are 50 DEG C, and two area's temperature of heating keep 40min, obtain gaseous MoO to 650 DEG C3-x, wherein 0<x ≤1；Three-temperature-zone is heated to 600 DEG C, 40min is kept；Two temperature-raising region temperature raising speed are 40 DEG C/min, and the heating rate of three-temperature-zone is 30 ℃/min；
Step 5, the 3rd heating period：Second heating period temperature reaches after stabilization that one warm area of heating is kept to 150 DEG C 40min, obtains sulfur vapor；Heating rate is 30 DEG C/min；High pure nitrogen flow velocity is adjusted to 60ccm, by carrier gas by the sulphur Steam, erbium chloride steam and the gaseous MoO3-xCarry to crucible reaction intracavitary, in substrate surface pre-nucleating；
Step 6, the 4th heating period：Two warm areas are heated to 950 DEG C, 40min is kept, three-temperature-zone is heated to 800 DEG C, Keep 40min；Two temperature-raising region temperature raising speed are 30 DEG C/min, and the heating rate of three-temperature-zone is 20 DEG C/min；Will by the carrier gas The sulfur vapor, erbium chloride steam and the gaseous MoO3-xCarried with molybdenum disulfide gas phase to crucible reaction intracavitary, in substrate Surface forms Er ions molybdenum disulfide film.
Step 7, the vacuum tube furnace of a warm area is opened, room temperature is naturally cooling to, stops the supply of sulphur source, two, three-temperature-zone Less than 500 DEG C are cooled under carrier gas protection, two, three-temperature-zone stove is opened, starts to be naturally cooling to room temperature.
Embodiment 3
Step 1, using three-temperature-zone chemical vapor deposition (CVD) system shown in Fig. 1, it is 99.99% sulphur powder to take purity 500mg is placed in corundum boat, is placed in a warm area；Purity is 99.99% molybdenum trioxide powder and purity is 99.99% erbium chloride Powder is placed in corundum boat, is placed in two warm areas；Wherein molybdenum trioxide silty amount is 15mg, and erbium chloride silty amount is 5mg；Choose C Surface sapphire or silica/silicon are cleaned as substrate, and to substrate；It is placed in quasi- closing crucible, then will after drying Crucible is placed on three-temperature-zone；
Step 2, the base vacuum in quartz ampoule is evacuated to below 1Pa using mechanical pump, into quartz ampoule in lead to inertia carry Gas：High pure nitrogen, the flow velocity for being passed through carrier gas is 100ccm, and flowing gas is cleaned for several times；
Step 3, the first heating period：Continue logical carrier gas, two warm areas are heated to 200 DEG C, three-temperature-zone is heated to 200 DEG C, keep 100min；The heating rate of two warm areas and three-temperature-zone is 15 DEG C/min；
Step 4, the second heating period：Inflation makes quartzy intraductal pressure reach after atmospheric pressure, adjusts carrier gas flux, sets two Warm area and three-temperature-zone temperature difference are 120 DEG C, and two area's temperature of heating keep 15min, obtain gaseous MoO to 720 DEG C3-x, wherein 0<x ≤1；Three-temperature-zone is heated to 600 DEG C, 15min is kept；Two temperature-raising region temperature raising speed are 50 DEG C/min, and the heating rate of three-temperature-zone is 40 ℃/min；
Step 5, the 3rd heating period：Second heating period temperature reaches after stabilization that one warm area of heating is kept to 170 DEG C 10min, obtains sulfur vapor；Heating rate is 35 DEG C/min；High pure nitrogen flow velocity is adjusted to 20ccm, by carrier gas by the sulphur Steam, erbium chloride steam and the gaseous MoO3-xCarry to crucible reaction intracavitary, in substrate surface pre-nucleating；
Step 6, the 4th heating period：Two warm areas are heated to 900 DEG C, 40min is kept, three-temperature-zone is heated to 850 DEG C, Keep 10min；Two temperature-raising region temperature raising speed are 18 DEG C/min, and the heating rate of three-temperature-zone is 25 DEG C/min；Will by the carrier gas The sulfur vapor, erbium chloride steam and the gaseous MoO3-xCarried with molybdenum disulfide gas phase to crucible reaction intracavitary, in substrate Surface forms Er ions molybdenum disulfide film.
Step 7, the vacuum tube furnace of a warm area is opened, room temperature is naturally cooling to, stops the supply of sulphur source, two, three-temperature-zone Less than 500 DEG C are cooled under carrier gas protection, two, three-temperature-zone stove is opened, starts to be naturally cooling to room temperature.
Embodiment 4
Step 1, using three-temperature-zone chemical vapor deposition (CVD) system shown in Fig. 1, it is 99.99% sulphur powder to take purity 700mg is placed in corundum boat, is placed in a warm area；Purity is 99.99% molybdenum trioxide powder and purity is 99.99% erbium chloride Powder is placed in corundum boat, is placed in two warm areas；Wherein molybdenum trioxide silty amount is 20mg, and erbium chloride silty amount is 5mg；Choose C Surface sapphire or silica/silicon are cleaned as substrate, and to substrate；It is placed in quasi- closing crucible, then will after drying Crucible is placed on three-temperature-zone；
Step 2, the base vacuum in quartz ampoule is evacuated to below 1Pa using mechanical pump, into quartz ampoule in lead to inertia carry Gas：High pure nitrogen, the flow velocity for being passed through carrier gas is 200ccm, and flowing gas is cleaned for several times；
Step 3, the first heating period：Continue logical carrier gas, two warm areas are heated to 250 DEG C, three-temperature-zone is heated to 250 DEG C, keep 150min；The heating rate of two warm areas and three-temperature-zone is 25 DEG C/min；
Step 4, the second heating period：Inflation makes quartzy intraductal pressure reach after atmospheric pressure, adjusts carrier gas flux, sets two Warm area and three-temperature-zone temperature difference are 150 DEG C, and two area's temperature of heating keep 20min, obtain gaseous MoO to 750 DEG C3-x, wherein 0<x ≤1；Three-temperature-zone is heated to 600 DEG C, 20min is kept；Two temperature-raising region temperature raising speed are 50 DEG C/min, and the heating rate of three-temperature-zone is 35 ℃/min；
Step 5, the 3rd heating period：Second heating period temperature reaches after stabilization that one warm area of heating is kept to 190 DEG C 30min, obtains sulfur vapor；Heating rate is 40 DEG C/min；High pure nitrogen flow velocity is adjusted to 20ccm, by carrier gas by the sulphur Steam, erbium chloride steam and the gaseous MoO3-xCarry to crucible reaction intracavitary, in substrate surface pre-nucleating；
Step 6, the 4th heating period：Two warm areas are heated to 900 DEG C, 40min is kept, three-temperature-zone is heated to 850 DEG C, Keep 30min；Two temperature-raising region temperature raising speed are 15 DEG C/min, and the heating rate of three-temperature-zone is 25 DEG C/min；Will by the carrier gas The sulfur vapor, erbium chloride steam and the gaseous MoO3-xCarried with molybdenum disulfide gas phase to crucible reaction intracavitary, in substrate Surface forms Er ions molybdenum disulfide film.
Step 7, the vacuum tube furnace of a warm area is opened, room temperature is naturally cooling to, stops the supply of sulphur source, two, three-temperature-zone Less than 500 DEG C are cooled under carrier gas protection, two, three-temperature-zone stove is opened, starts to be naturally cooling to room temperature.
Embodiment 5
Step 1, using three-temperature-zone chemical vapor deposition (CVD) system shown in Fig. 1, it is 99.99% sulphur powder to take purity 900mg is placed in corundum boat, is placed in a warm area；Purity is 99.99% molybdenum trioxide powder and purity is 99.99% erbium chloride Powder is placed in corundum boat, is placed in two warm areas；Wherein molybdenum trioxide silty amount is 18mg, and erbium chloride silty amount is 3mg；Choose C Surface sapphire or silica/silicon are cleaned as substrate, and to substrate；It is placed in quasi- closing crucible, then will after drying Crucible is placed on three-temperature-zone；
Step 2, the base vacuum in quartz ampoule is evacuated to below 1Pa using mechanical pump, into quartz ampoule in lead to inertia carry Gas：High pure nitrogen, the flow velocity for being passed through carrier gas is 400ccm, and flowing gas is cleaned for several times；
Step 3, the first heating period：Continue logical carrier gas, two warm areas are heated to 300 DEG C, three-temperature-zone is heated to 300 DEG C, keep 80min；The heating rate of two warm areas and three-temperature-zone is 30 DEG C/min；
Step 4, the second heating period：Inflation makes quartzy intraductal pressure reach after atmospheric pressure, adjusts carrier gas flux, sets two Warm area and three-temperature-zone temperature difference are 400 DEG C, and two area's temperature of heating keep 10min, obtain gaseous MoO to 800 DEG C3-x, wherein 0<x ≤1；Three-temperature-zone is heated to 700 DEG C, 10min is kept；Two temperature-raising region temperature raising speed are 50 DEG C/min, and the heating rate of three-temperature-zone is 40 ℃/min；
Step 5, the 3rd heating period：Second heating period temperature reaches after stabilization that one warm area of heating is kept to 200 DEG C 20min, obtains sulfur vapor；Heating rate is 45 DEG C/min；High pure nitrogen flow velocity is adjusted to 40ccm, by carrier gas by the sulphur Steam, erbium chloride steam and the gaseous MoO3-xCarry to crucible reaction intracavitary, in substrate surface pre-nucleating；
Step 6, the 4th heating period：Two warm areas are heated to 850 DEG C, 20min is kept, three-temperature-zone is heated to 800 DEG C, Keep 20min；Two temperature-raising region temperature raising speed are 5 DEG C/min, and the heating rate of three-temperature-zone is 10 DEG C/min；By the carrier gas by institute State sulfur vapor, erbium chloride steam and the gaseous MoO3-xCarried with molybdenum disulfide gas phase to crucible reaction intracavitary, in substrate table Face forms Er ions molybdenum disulfide film.
Step 7, the vacuum tube furnace of a warm area is opened, room temperature is naturally cooling to, stops the supply of sulphur source, two, three-temperature-zone Less than 500 DEG C are cooled under carrier gas protection, two, three-temperature-zone stove is opened, starts to be naturally cooling to room temperature.
Embodiment 6
Step 1, using three-temperature-zone chemical vapor deposition (CVD) system shown in Fig. 1, it is 99.99% sulphur powder to take purity 1000mg is placed in corundum boat, is placed in a warm area；Purity is 99.99% molybdenum trioxide powder and purity is 99.99% chlorination Erbium powder is placed in corundum boat, is placed in two warm areas；Wherein molybdenum trioxide silty amount is 4mg, and erbium chloride silty amount is 4mg；Choose C Surface sapphire or silica/silicon are cleaned as substrate, and to substrate；It is placed in quasi- closing crucible, then will after drying Crucible is placed on three-temperature-zone；
Step 2, the base vacuum in quartz ampoule is evacuated to below 1Pa using mechanical pump, into quartz ampoule in lead to inertia carry Gas：High pure nitrogen, the flow velocity for being passed through carrier gas is 400ccm, and flowing gas is cleaned for several times；
Step 3, the first heating period：Continue logical carrier gas, two warm areas are heated to 350 DEG C, three-temperature-zone is heated to 350 DEG C, keep 60min；The heating rate of two warm areas and three-temperature-zone is 35 DEG C/min；
Step 4, the second heating period：Inflation makes quartzy intraductal pressure reach after atmospheric pressure, adjusts carrier gas flux, sets two Warm area and three-temperature-zone temperature difference are 200 DEG C, and two area's temperature of heating keep 10min, obtain gaseous MoO to 800 DEG C3-x, wherein 0<x ≤1；Three-temperature-zone is heated to 600 DEG C, 10min is kept；Two temperature-raising region temperature raising speed are 20 DEG C/min, and the heating rate of three-temperature-zone is 15 ℃/min；
Step 5, the 3rd heating period：Second heating period temperature reaches after stabilization that one warm area of heating is kept to 220 DEG C 10min, obtains sulfur vapor；Heating rate is 50 DEG C/min；High pure nitrogen flow velocity is adjusted to 30ccm, by carrier gas by the sulphur Steam, erbium chloride steam and the gaseous MoO3-xCarry to crucible reaction intracavitary, in substrate surface pre-nucleating；
Step 6, the 4th heating period：Two warm areas are heated to 950 DEG C, 10min is kept, three-temperature-zone is heated to 900 DEG C, Keep 10min；Two temperature-raising region temperature raising speed are 15 DEG C/min, and the heating rate of three-temperature-zone is 50 DEG C/min；Will by the carrier gas The sulfur vapor, erbium chloride steam and the gaseous MoO3-xCarried with molybdenum disulfide gas phase to crucible reaction intracavitary, in substrate Surface forms Er ions molybdenum disulfide film.
Step 7, the vacuum tube furnace of a warm area is opened, room temperature is naturally cooling to, stops the supply of sulphur source, two, three-temperature-zone Less than 500 DEG C are cooled under carrier gas protection, two, three-temperature-zone stove is opened, starts to be naturally cooling to room temperature.
A kind of preparation method of Er ions molybdenum disulfide film of the present invention has the following advantages：The chemical gas in three-temperature-zone is used Phase depositing system is independently controlled to molybdenum source evaporating temperature, erbium source evaporating temperature and growth temperature, realizes accurate control not With the parameter of growth phase.The outstanding advantages of this method are to evaporate erbium chloride and molybdenum trioxide jointly simultaneously, obtain the two Gas phase, the large area deposition of Er ions molybdenum disulfide is realized by gas phase mixing；In addition, substrate is placed in quasi- closing crucible, The molybdenum erbium source into inside crucible is greatly reduced, the preparation for individual layer Er ions molybdenum disulfide film provides condition.

Claims (9)

1. a kind of preparation method of Er ions molybdenum disulfide film, it is characterised in that comprise the following steps：
Step 1, using three-temperature-zone chemical gas-phase deposition system, sulphur powder is placed in a warm area；By molybdenum trioxide powder and erbium chloride powder It is placed in two warm areas；Crucible bottom with cover is placed the substrate in, crucible is then placed on three-temperature-zone；
Step 2, will be vacuumized in quartz ampoule, into quartz ampoule in lead to carrier gas and cleaned；
Step 3, the first heating period：Continue to lead to the carrier gas, two warm areas are heated to 150~350 DEG C, keep 60~ 180min；Three-temperature-zone is heated to 150~350 DEG C, 60~180min is kept；
Step 4, the second heating period：Inflation make quartzy intraductal pressure be atmospheric pressure after, adjust carrier gas flux, set two warm areas and Three-temperature-zone temperature difference is 0~200 DEG C, and two area's temperature of heating keep 10~60min, obtain gaseous MoO to 580~800 DEG C3-x, Wherein 0<x≤1；Three-temperature-zone is heated to 580~700 DEG C, 10~60min is kept；
Step 5, the 3rd heating period：A warm area is heated to 130~220 DEG C, 10~60min is kept, obtains sulfur vapor；
Step 6, the 4th heating period：Two warm areas are heated to 800 DEG C~950 DEG C, 10~60min is kept；Three-temperature-zone is heated To 750 DEG C~900 DEG C, 10~60min is kept；By the carrier gas by the sulfur vapor, erbium chloride steam and described gaseous MoO3-xCarry to crucible reaction intracavitary, in substrate surface formation Er ions molybdenum disulfide film.
2. the preparation method of a kind of Er ions molybdenum disulfide film according to claim 1, it is characterised in that in step 1 Sulphur powder and the mass ratio of molybdenum trioxide powder are：20：1~250:1；The mass ratio of molybdenum trioxide powder and erbium chloride is：1：1~6：1.
3. the preparation method of a kind of Er ions molybdenum disulfide film according to claim 1, it is characterised in that in step 1 The substrate is silica, carborundum, silicon or sapphire.
4. the preparation method of a kind of Er ions molybdenum disulfide film according to claim 1, it is characterised in that in step 2 The carrier gas is high pure nitrogen, argon gas, dilution hydrogen or high purity inert gas, and the flow velocity for being passed through carrier gas is 100~500ccm.
5. the preparation method of a kind of Er ions molybdenum disulfide film according to claim 1, it is characterised in that in step 5 The flow rate of carrier gas is adjusted to 10~80ccm.
6. the preparation method of a kind of Er ions molybdenum disulfide film according to claim 1, it is characterised in that in step 3 The heating rate of the warm area of first heating period two and three-temperature-zone is 10~35 DEG C/min.
7. the preparation method of a kind of Er ions molybdenum disulfide film according to claim 1, it is characterised in that in step 4 The heating rate of the warm area of second heating period two and three-temperature-zone is 15~50 DEG C/min.
8. the preparation method of a kind of Er ions molybdenum disulfide film according to claim 1, it is characterised in that in step 5 The heating rate of the warm area of 3rd heating period one is 20~40 DEG C/min.
9. the preparation method of a kind of Er ions molybdenum disulfide film according to claim 1, it is characterised in that in step 6 The heating rate of the warm area of 4th heating period two and three-temperature-zone is 5~50 DEG C/min.
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CN108286042A (en) * 2018-03-19 2018-07-17 西北大学 A kind of number of plies is uniformly and the preparation method of high quality molybdenum disulfide film
CN110055591A (en) * 2019-05-17 2019-07-26 中国科学院物理研究所 The preparation method of two-dimentional ternary atomic crystal
CN110568546A (en) * 2019-08-21 2019-12-13 北京大学 Preparation method of transition metal chalcogenide composite optical fiber material
CN110735127A (en) * 2018-07-18 2020-01-31 中国科学院宁波材料技术与工程研究所 molybdenum disulfide self-lubricating composite coating, and preparation method and application thereof
CN110777356A (en) * 2019-11-12 2020-02-11 天津理工大学 Rare earth doped molybdenum sulfide monomolecular layer film and preparation method thereof
CN112760613A (en) * 2019-10-21 2021-05-07 浙江大学 Preparation method of carbon-doped molybdenum disulfide nano material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108286042A (en) * 2018-03-19 2018-07-17 西北大学 A kind of number of plies is uniformly and the preparation method of high quality molybdenum disulfide film
CN110735127A (en) * 2018-07-18 2020-01-31 中国科学院宁波材料技术与工程研究所 molybdenum disulfide self-lubricating composite coating, and preparation method and application thereof
CN110735127B (en) * 2018-07-18 2021-09-28 中国科学院宁波材料技术与工程研究所 Molybdenum disulfide self-lubricating composite coating and preparation method and application thereof
CN110055591A (en) * 2019-05-17 2019-07-26 中国科学院物理研究所 The preparation method of two-dimentional ternary atomic crystal
CN110568546A (en) * 2019-08-21 2019-12-13 北京大学 Preparation method of transition metal chalcogenide composite optical fiber material
CN110568546B (en) * 2019-08-21 2020-06-09 北京大学 Preparation method of transition metal chalcogenide composite optical fiber material
CN112760613A (en) * 2019-10-21 2021-05-07 浙江大学 Preparation method of carbon-doped molybdenum disulfide nano material
CN112760613B (en) * 2019-10-21 2021-11-09 浙江大学 Preparation method of carbon-doped molybdenum disulfide nano material
CN110777356A (en) * 2019-11-12 2020-02-11 天津理工大学 Rare earth doped molybdenum sulfide monomolecular layer film and preparation method thereof

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