CN101696492B - Device and method for preparing aluminum-doped zinc oxide transparent conductive film - Google Patents
Device and method for preparing aluminum-doped zinc oxide transparent conductive film Download PDFInfo
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- CN101696492B CN101696492B CN2009102365150A CN200910236515A CN101696492B CN 101696492 B CN101696492 B CN 101696492B CN 2009102365150 A CN2009102365150 A CN 2009102365150A CN 200910236515 A CN200910236515 A CN 200910236515A CN 101696492 B CN101696492 B CN 101696492B
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Abstract
The invention discloses a device and a method for preparing an aluminum-doped zinc oxide transparent conductive film. The device is improved aiming at the prior metal organic chemical vapor deposition (MOCVD) equipment, and the improved MOCVD is provided with a zinc source gas circuit and an oxygen source gas circuit, wherein the zinc source gas circuit is used for providing a film-forming raw material, and the oxygen source gas circuit is used for providing hot water vapor in the process of processing the film. When the film is prepared, zinc acetylacetonate Zn(C5H7O2)2.H2O and aluminum acetylacetonate Al(C5H7O2)3 are taken as a zinc source and an aluminum source respectively, distilled water is taken as an oxygen source, nitrogen is taken as carrier gas, and the film is formed under the conditions with no vacuum equipment, atmospheric environment and a processing temperature of between 170 and 270 DEG C. The method has a simple film-forming process and a low deposition temperature, is favorable for the industrial production of the transparent conductive film, and reduces the production cost.
Description
Technical field
The present invention relates to a kind of metal organic chemical vapor deposition device, more particularly say, be meant a kind of atmosphere opening formula MOCVD device, and adopt atmosphere opening formula MOCVD device under 170 ℃～270 ℃ environment of lesser temps, carry out the method for aluminum-doped zinc oxide transparent conductive film preparation.
Background technology
Transparent conductive oxide is one of mainstay of opto-electronics, and transparent conductive film is widely used in aspects such as sun power transparency electrode, plasma body liquid-crystal display and Energy Saving Windows especially.ITO (indium tin oxide) has lost its absolute leading advantage gradually owing to the shortage of indium resource and the needs of environmental protection.The transparent conductive film of Zinc oxide-base is just becoming the surrogate of ITO because its rich natural resource and the photoelectric characteristic that can match in excellence or beauty with ITO.Traditional method for preparing transparent conductive film comprises pulsed laser deposition (PLD), molecular beam epitaxy (MBE), metal organic chemical vapor deposition (MOCVD), atomic layer epitaxy (ALE), sputter (comprising magnetron sputtering and d.c. sputtering), chemical meteorology deposition (CVD), electron beam evaporation, shoots out pyrolysis, collosol and gel (Sol-gel) or the like, these equipment are in the process of preparation transparent conductive film, all to use vacuum apparatus, and film-forming temperature higher (generally at 300 ℃～500 ℃), the film forming area is little.
Summary of the invention
One of purpose of the present invention provides a kind of atmosphere opening formula metal organic chemical vapor deposition (MOCVD) device, and this device is the improvement that existing metal organic chemical vapor deposition (MOCVD) equipment is carried out.MOCVD after the improvement has zinc source gas circuit and oxygen source gas circuit, and zinc source gas circuit is used to be provided as the pleurodiaphragmatic in terspace material, the water vapour of the heat when the oxygen source gas circuit is used to processing of films is provided.Because during processing system film is atmospheric environment, needing no vacuum equipment makes and carries out the processing of aluminum-doped zinc oxide transparent conductive film with MOCVD device of the present invention, and is with low cost, be easy to moulding.Because of 170 ℃～270 ℃ of processing temperatures are lower, enlarged the choice of substrate scope again.
The preparation of the aluminum-doped zinc oxide transparent conductive film that the device of application the present invention design carries out is with zinc acetylacetonate Zn (C
5H
7O
2)
2H
2O and aluminium acetylacetonate Al (C
5H
7O
2)
3Being respectively zinc source and aluminium source, is oxygen source with distilled water, and nitrogen is carrier gas, and the step of the adulterated zinc oxide transparent conductive film of preparation aluminium has:
(A) substrate is handled
Choose glass substrate, and be put into successively in acetone (mass percent concentration is 99%), dehydrated alcohol (mass percent concentration is 99%) and the deionized water, remove the dirt of substrate surface respectively behind ultrasonic cleaning cleaning 15min～20min, substrate after will cleaning is then put into the loft drier of 35 ℃～50 ℃ of drying temperatures, behind oven dry 15～20min, take out stand-by;
(B) mould material preparation
With zinc acetylacetonate Zn (C
5H
7O
2)
2H
2O and aluminium acetylacetonate Al (C
5H
7O
2)
3Grind and make the mould material that granularity is 10 μ m～50 μ m, and mould material is placed vaporizer 5;
Zn (the C that adds 9.40g～9.88g in the mould material of consumption: 10g
5H
7O
2)
2H
2Al (the C of O and 0.12g～0.60g
5H
7O
2)
3
(C) preheating of gas channels
(D) logical in advance N
2
When treating that vaporizer 5 temperature rise to 80 ℃～105 ℃, open the master switch on the nitrogengas cylinder 1, low pressure valve is transferred to 0.3MPa～0.5MPa;
Open then on the A pipeline 21 by air valve 2A, respectively with the flow rate regulation of the first flow meter 3A and the second under meter 3B to 0.3L/min～0.4L/min, the foreign gas in the gas channels is got rid of;
(E) treat that vaporizer 5 temperature reach 105 ℃～115 ℃, substrate temperature and reach that medium temperatures reach 80 ℃～100 ℃ in 170 ℃～270 ℃ and the flask 11, and guarantee that each parameter after 15min is with interior maintenance balance and stability state, closes the first flow meter 3A and the second under meter 3B;
Substrate with oven dry is installed on the chip bench 9 then;
(F) open the first flow meter 3A and the second under meter 3B once more, and the flow velocity of regulating first flow meter 3A is 0.6L/min～1.2L/min, the flow velocity of the second under meter 3B is 0.1L/min～0.4L/min; Set depositing time 120min, vapour deposition begins;
(G) behind the vapour deposition result, stop heating successively, stop logical nitrogen at last, thereby make the adulterated zinc oxide transparent conductive film of aluminium preheating zone, insulation belt and vaporizer.
Take off the substrate that deposits conductive film from chip bench 9 and carry out the analysis of every performance.
The advantage of a kind of atmosphere opening formula MOCVD device of the present invention is:
(1) this device can be implemented in film forming under atmospheric environment, low 170 ℃～270 ℃ temperature, and film-forming process is controlled.
(2) owing to carry out film forming at a lower temperature, feasible village's matter to the one-tenth film substrate is less demanding, can be implemented in and carry out film forming on the multiple substrate.
(3) in the film forming preparation process,, make that the film performance that makes is more superior by controlling zinc source gas circuit flow, oxygen source gas circuit flow flexibly.
(4) it is low to adopt device of the present invention to prepare transparent conductive film requiring on equipment than traditional MOCVD method, need not high vacuum apparatus, and operating process is simple, and depositing temperature is low, effectively reduces production cost.The industrialization production that this obviously helps transparent conductive film has significant values to applying of transparent conductive film.
Description of drawings
Fig. 1 is the structure iron of atmosphere opening formula MOCVD device of the present invention.
Fig. 2 is the XRD figure spectrum of the product that makes of embodiment 1.
Fig. 3 is the SEM picture of the product that makes of embodiment 1.
Fig. 4 is the transmittance curve of the product that makes of embodiment 1.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
See also shown in Figure 1, a kind of atmosphere opening formula metal organic chemical vapor deposition (MOCVD) device for preparing aluminum-doped zinc oxide transparent conductive film of the present invention includes first by air valve 2A, second by air valve 2B, A pipeline 21, B pipeline 22, C pipeline 23, D pipeline 24, E pipeline 25, F pipeline 26, G pipeline 27, nitrogengas cylinder 1, first flow meter 3A, the second under meter 3B, molecular sieve 4, vaporizer 5, the first heating zone 6A, the second heating zone 6B, the 3rd heating zone 6C, the first nozzle 7A, the second nozzle 7B, substrate 8, chip bench 9, well heater 10 and flask 11; Substrate 8 is placed on the chip bench 9;
Flask 11 is installed on the well heater 10, and well heater 10 can provide 80 ℃～100 ℃ temperature environment for the distilled water of placing in the flask 11;
The first heating zone 6A is wrapped in the outer wall of C pipeline 23 and the outer wall of vaporizer 5, and the first heating zone 6A can provide 105 ℃～115 ℃ temperature environment for the medium of C pipeline 23 and vaporizer 5 inside.Be connected with first voltate regulator on the first heating zone 6A, the outer wall of the outer wall of C pipeline 23 and vaporizer 5 is equipped with first thermopair that is used to measure temperature when twining the first heating zone 6A, the thermometric end of this thermopair is close to the outer wall of vaporizer 5, the terminals of this thermopair are connected on the temperature display meter, carry out design temperature operation (instrument is a single input channel digital intelligent instrument, model XST/D-F, sky, Beijing Chen Zidonghuayibiaochang) by the instrument keyboard.
The second heating zone 6B is wrapped in the outer wall of D pipeline 24, and the second heating zone 6B can provide 105 ℃～150 ℃ temperature environment for the medium of D pipeline 24 inside.On the outer wall of the D pipeline 24 between vaporizer 5 to the first nozzle 7A, be wound with the second heating zone 6B, be connected with second voltate regulator on the second heating zone 6B, second thermopair that is used to measure temperature is installed when twining the second heating zone 6B, the thermometric end of this thermopair is close to the outer wall of D pipeline 24, the terminals of this thermopair are connected (instrument is a single input channel digital intelligent instrument, model XST/D-F, sky, Beijing Chen Zidonghuayibiaochang) on the temperature display meter.
The 3rd heating zone 6C is wrapped in the outer wall of E pipeline 25, and the 3rd heating zone 6C can provide 80 ℃～100 ℃ temperature environment for the medium of E pipeline 25 inside.On the outer wall of the E pipeline 25 between the flask 10 and the second nozzle 7B, be wound with the 3rd heating zone 6C, be connected with the 3rd voltate regulator on the 3rd heating zone 6C, the three thermocouple that is used to measure temperature is installed when twining the 3rd heating zone 6C, the thermometric end of this thermopair is close to the outer wall of E pipeline 25, the terminals of this thermopair are connected (instrument is a single input channel digital intelligent instrument, model XST/D-F, sky, Beijing Chen Zidonghuayibiaochang) on the temperature display meter.
Wherein, nitrogengas cylinder 1, A pipeline 21, first end air valve 2A and molecular sieve 4 formation carrier gas source.A pipeline 21 is connected between the air intake of the delivery port of nitrogengas cylinder 1 and molecular sieve 4, and is equipped with first on the A pipeline 21 by air valve 2A.
Wherein, B pipeline 22, first flow meter 3A, C pipeline 23, the first heating zone 6A, vaporizer 5, second end air valve 2B, the second heating zone 6B and D pipeline 24 formation zinc source gas circuits.B pipeline 22 is connected between the air intake of air outlet of molecular sieve 4 and first flow meter 3A, C pipeline 23 is connected between the air intake of the air outlet of first flow meter 3A and vaporizer 5, D pipeline 24 is connected between the air outlet and the first nozzle 7A of vaporizer 5, and is equipped with second on the D pipeline 24 by air valve 2B.
Wherein, G pipeline 27, the second under meter 3B, F pipeline 26, well heater 10, flask 11, the 3rd heating zone 6C and E pipeline 25 constitute the oxygen source gas circuit.G pipeline 27 is connected between the air intake of another air outlet of molecular sieve 4 and the second under meter 3B, F pipeline 26 is connected between the bottleneck of the air outlet of the second under meter 3B and flask 11, and E pipeline 25 is connected between another bottleneck and the second nozzle 7B of flask 11.
The preparation method of the atmosphere opening formula MOCVD device of application the present invention design, the aluminum-doped zinc oxide transparent conductive film that carries out includes following steps:
(A) substrate is handled
At first the substrate of choosing is put into the vessel that acetone (mass percent concentration is 99%) is housed, put into vessel and take out after ultrasonic cleaner cleans 15～20min;
Put into the vessel that dehydrated alcohol (mass percent concentration is 99%) is housed then, put into vessel and take out after ultrasonic cleaner cleans 15～20min;
Put into the vessel that deionized water is housed then, put into vessel and take out the substrate after obtaining cleaning after ultrasonic cleaner cleans 15～20min;
At last cleaning substrate is put in the Constant Temp. Oven, under the condition of 35 ℃～50 ℃ of drying temperatures, obtained the substrate of dry cleansing behind oven dry 15～20min, stand-by;
(B) mould material preparation
With zinc acetylacetonate Zn (C
5H
7O
2)
2H
2O and aluminium acetylacetonate Al (C
5H
7O
2)
3Grind and make the mould material that granularity is 10 μ m～50 μ m, and mould material is placed vaporizer 5;
Zn (the C that adds 9.40g～9.88g in the mould material of consumption: 10g
5H
7O
2)
2H
2Al (the C of O and 0.12g～0.60g
5H
7O
2)
3
(C) preheating of gas channels
(D) logical in advance N
2
When treating that vaporizer 5 temperature reach 80 ℃～105 ℃, open the master switch on the nitrogengas cylinder 1, low pressure valve is transferred to 0.3MPa～0.5MPa;
Open subsequently on the A pipeline 21 by air valve 2A, and the flow velocity of regulating the first flow meter 3A and the second under meter 3B is 0.3L/min～0.4L/min; In passage, feed nitrogen, the foreign gas in the gas channels is got rid of.
In the present invention, by on molecular sieve 4, connecting the first flow meter 3A and the second under meter 3B respectively, and the passage of first flow meter 3A to the first nozzle 7A, second under meter 3B to the second nozzle 7B passage, carrier gas (nitrogen) is split into two-way, one the tunnel is zinc source gas circuit, and another road is the oxygen source gas circuit.
Described zinc source gas circuit is because the raw material zinc acetylacetonate Zn (C of vapour deposition is arranged in vaporizer 5
5H
7O
2)
2H
2O and aluminium acetylacetonate Al (C
5H
7O
2)
3, under 105 ℃～115 ℃ of certain temperature, protective atmosphere (nitrogen), after first nozzle 7A ejection, be deposited on the substrate.
Described oxygen source gas circuit, the hot water and steam blending that nitrogen and distilled water form under 80 ℃～100 ℃ temperature makes nitrogen carry hot water and steam and is sprayed by the second nozzle 7B.
In the present invention, nitrogen carries hot water and steam and film forming raw material thorough mixing above substrate 8, makes that the aluminum-doped zinc oxide transparent conductive film that is deposited on the substrate 8 is evenly fine and close, has improved perviousness, the electroconductibility of film effectively.
(E) treat that vaporizer 5 temperature reach 105 ℃～115 ℃, substrate temperature and reach that medium temperatures reach 80 ℃～100 ℃ in 170 ℃～270 ℃ and the flask 11, and guarantee that each parameter is after 15min is with interior maintenance balance and stability state, close the first flow meter 3A and the second under meter 3B, and the substrate of dry cleansing is installed on the chip bench 9;
(F) open the first flow meter 3A and the second under meter 3B once more, and the flow velocity of regulating first flow meter 3A is 0.6L/min～1.2L/min, the flow velocity of the second under meter 3B is 0.1L/min～0.4L/min; Set depositing time 120min, vapour deposition begins;
(G) behind the vapour deposition result, stop heating successively, stop logical nitrogen at last, thereby make the adulterated zinc oxide transparent conductive film of aluminium preheating zone, insulation belt and vaporizer.
In order to analyze every performance of the adulterated zinc oxide transparent conductive film of aluminium, the contriver adopts XRD, SEM, visible region transmitance etc. to carry out performance test.
Embodiment 1:
Substrate: glass substrate 2cm * 2.5cm * 0.1cm
Film forming thickness: 400nm
(A) substrate is handled
It is that 99% acetone, mass percent concentration are in 99% the dehydrated alcohol and deionized water that the glass substrate of choosing is put into mass percent concentration successively, in ultrasonic cleaner, clean the dirt that 15min removes substrate surface respectively, after the cleaning substrate is put in the Constant Temp. Oven, under the condition of 40 ℃ of drying temperatures, behind the oven dry 15min, take out stand-by;
(B) mould material preparation
Zn (C with 1.405g
5H
7O
2)
2H
2Al (the C of O and 0.050g
5H
7O
2)
3Grind and make the mould material that 80% granularity is 30 μ m, and mould material is placed vaporizer 5;
(C) preheating of gas channels
(D) logical in advance N
2
When treating that vaporizer 5 temperature rise to 100 ℃, open the master switch on the nitrogengas cylinder 1, low pressure valve is transferred to 0.3MPa, open on the A pipeline 21 by air valve 2A, regulate the first flow meter 3A and the second under meter 3B, flow velocity is adjusted to 0.3L/min, the foreign gas in the gas channels is got rid of;
(E) treat that vaporizer 5 temperature are that 100 ℃, substrate temperature are 220 ℃, and medium (distilled water) temperature is 80 ℃ in the flask 11, and guarantee that each parameter after 15min is with interior maintenance balance and stability state, closes the first flow meter 3A and the second under meter 3B, and the substrate of oven dry is placed on the chip bench 9;
(F) open the first flow meter 3A and the second under meter 3B once more, and the flow velocity of regulating first flow meter 3A is 0.8L/min, the flow velocity of the second under meter 3B is 0.2L/min; Vapour deposition begins, and the setting depositing time is 120min;
(G) after depositing time reaches preset time 120min, close the control power supply of preheating zone, insulation belt and vaporizer, all switches and the device power supply (DPS) on the control panel successively, and stop logical nitrogen.
(H) take out sample and carry out the XRD diffraction, SEM pattern, the performance test of visible region transmitance and square resistance.
Referring to shown in Figure 2, be the XRD diffracting spectrum of the aluminum-doped zinc oxide transparent conductive film that makes of the preparation method through embodiment 1.Among the figure, the zincite crystal crystallization degree is very high, has hexagonal wurtzite structure and edge (002) direction preferential growth.
Referring to shown in Figure 3, be the SEM pattern photo of the aluminum-doped zinc oxide transparent conductive film that makes of the preparation method through embodiment 1.Among the figure, film is the nano-multicrystal film, and growth is fine and close, even, and no big defectives such as hole have microstructure preferably, and crystal grain is tiny, spherical in shape, and diameter is 100nm～150nm.
Referring to shown in Figure 4, be the visible region transmittance curve figure of the aluminum-doped zinc oxide transparent conductive film that makes of the preparation method through embodiment 1.Among the figure, film can reach more than 90% at the average transmittances of visible region, has good perviousness.
Square resistance through the aluminum-doped zinc oxide transparent conductive film that the preparation method of embodiment 1 makes is to test under the condition that two electrical measurement four point probe resistance meters are 1mA at outward current by the SDY-6 type, and its square resistance is 24 Ω.
Embodiment 2:
Substrate: alumina substrate 5cm * 3cm * 0.5cm of 95%
Film forming thickness: 500nm
(A) substrate is handled
With 95% the alumina substrate of choosing, it is cut into the carrier of required size, be put into mass percent concentration successively and be 99% acetone, mass percent concentration and be in 99% the dehydrated alcohol and deionized water, in ultrasonic cleaner, clean the dirt that 20min removes substrate surface respectively, after the cleaning substrate is put in the Constant Temp. Oven, under the condition of 50 ℃ of drying temperatures, behind the oven dry 20min, take out stand-by;
(B) mould material preparation
Zn (C with 1.405g
5H
7O
2)
2H
2Al (the C of O and 0.033g
5H
7O
2)
3Grind and make the mould material that 80% granularity is 40 μ m, and mould material is placed vaporizer 5;
(C) preheating of gas channels
(D) logical in advance N
2
When treating that vaporizer 5 temperature rise to 100 ℃, open the master switch on the nitrogengas cylinder 1, low pressure valve is transferred to 0.3MPa, open on the A pipeline 21 by air valve 2A, regulate the first flow meter 3A and the second under meter 3B, flow velocity is adjusted to 0.3L/min, the foreign gas in the gas channels is got rid of;
(E) treat that vaporizer 5 temperature are that 100 ℃, substrate temperature are 270 ℃, and medium temperature is 80 ℃ in the flask 11, and guarantee that each parameter after 15min is with interior maintenance balance and stability state, closes the first flow meter 3A and the second under meter 3B, and the substrate of oven dry is placed on the chip bench 9;
(F) open the first flow meter 3A and the second under meter 3B once more, and the flow velocity of regulating first flow meter 3A is 1.2L/min, the flow velocity of the second under meter 3B is 0.3L/min; Vapour deposition begins, and the setting depositing time is 120min;
(G) after depositing time reaches preset time 120min, close the control power supply of preheating zone, insulation belt and vaporizer, all switches and the device power supply (DPS) on the control panel successively, and stop logical nitrogen.
Square resistance through the aluminum-doped zinc oxide transparent conductive film that the preparation method of embodiment 2 makes is to test under the condition that two electrical measurement four point probe resistance meters are 1mA at outward current by the SDY-6 type, and its square resistance is 208 Ω.
Embodiment 3:
Substrate: polyethylene terephthalate substrate 1cm * 2cm * 0.1cm
Film forming thickness: 100nm
(A) substrate is handled
Choose glass substrate, be cut into the carrier of required size, be put into mass percent concentration successively and be 99% acetone, mass percent concentration and be in 99% the dehydrated alcohol and deionized water, in ultrasonic cleaner, clean the dirt that 15min removes substrate surface respectively, after the cleaning substrate is put in the Constant Temp. Oven, under the condition of 50 ℃ of drying temperatures, behind the oven dry 15min, take out stand-by;
(B) mould material preparation
Zn (C with 1.405g
5H
7O
2)
2H
2Al (the C of O and 0.050g
5H
7O
2)
3Grind and make the mould material that 80% granularity is 40 μ m, and mould material is placed vaporizer 5;
(C) preheating of gas channels
(D) logical in advance N
2
When treating that vaporizer 5 temperature rise to 100 ℃, open the master switch on the nitrogengas cylinder 1, low pressure valve is transferred to 0.3MPa, open on the A pipeline 21 by air valve 2A, regulate the first flow meter 3A and the second under meter 3B, flow velocity is adjusted to 0.3L/min, the foreign gas in the gas channels is got rid of.
(E) treat that vaporizer 5 temperature are that 100 ℃, substrate temperature are 170 ℃, and medium temperature is 80 ℃ in the flask 11, and guarantee that each parameter after 15min is with interior maintenance balance and stability state, closes the first flow meter 3A and the second under meter 3B, and the substrate of oven dry is placed on the chip bench 9;
(F) open the first flow meter 3A and the second under meter 3B once more, and the flow velocity of regulating first flow meter 3A is 1.0L/min, the flow velocity of the second under meter 3B is 0.2L/min; Vapour deposition begins, and the setting depositing time is 120min;
(G) after depositing time reaches preset time 120min, close the control power supply of preheating zone, insulation belt and vaporizer, all switches and the device power supply (DPS) on the control panel successively, and stop logical nitrogen.
The visible region average transmittances of the aluminum-doped zinc oxide transparent conductive film that makes through the preparation method of embodiment 3 can reach 80%.
Square resistance through the aluminum-doped zinc oxide transparent conductive film that the preparation method of embodiment 3 makes is to test under the condition that two electrical measurement four point probe resistance meters are 1mA at outward current by the SDY-6 type, and its square resistance is 440 Ω.
Claims (5)
1. atmosphere opening formula MOCVD device for preparing aluminum-doped zinc oxide transparent conductive film is characterized in that:
Include first by air valve (2A), second by air valve (2B), A pipeline (21), B pipeline (22), C pipeline (23), D pipeline (24), E pipeline (25), F pipeline (26), G pipeline (27), nitrogengas cylinder (1), first flow meter (3A), second under meter (3B), molecular sieve (4), vaporizer (5), first heating zone (6A), second heating zone (6B), the 3rd heating zone (6C), first nozzle (7A), second nozzle (7B), chip bench (9), well heater (10) and flask (11);
Chip bench (9) is gone up and is placed substrate (8);
Flask (11) is installed on the well heater (10), and well heater (10) can provide 80 ℃～100 ℃ temperature environment for the distilled water of placing in the flask (11);
First heating zone (6A) is wrapped in the outer wall of C pipeline (23) and the outer wall of vaporizer (5), and first heating zone (6A) can provide 105 ℃～115 ℃ temperature environment for the medium of C pipeline (23) and vaporizer (5) inside;
Second heating zone (6B) is wrapped in the outer wall of D pipeline (24), and second heating zone (6B) can provide 105 ℃～150 ℃ temperature environment for the inner medium of D pipeline (24);
The 3rd heating zone (6C) is wrapped in the outer wall of E pipeline (25), and the 3rd heating zone (6C) can provide 80 ℃～100 ℃ temperature environment for the inner medium of E pipeline (25);
Nitrogengas cylinder (1), A pipeline (21), first constitute carrier gas source by air valve (2A) and molecular sieve (4); A pipeline (21) is connected between the air intake of the delivery port of nitrogengas cylinder (1) and molecular sieve (4), and is equipped with first on the A pipeline (21) by air valve (2A);
B pipeline (22), first flow meter (3A), C pipeline (23), first heating zone (6A), vaporizer (5), second constitute zinc source gas circuit by air valve (2B), second heating zone (6B) and D pipeline (24); B pipeline (22) is connected between the air intake of air outlet of molecular sieve (4) and first flow meter (3A), C pipeline (23) is connected between the air intake of the air outlet of first flow meter (3A) and vaporizer (5), D pipeline (24) is connected between the air outlet and first nozzle (7A) of vaporizer (5), and is equipped with second on the D pipeline (24) by air valve (2B);
G pipeline (27), second under meter (3B), F pipeline (26), well heater (10), flask (11), the 3rd heating zone (6C) and E pipeline (25) constitute the oxygen source gas circuit; G pipeline (27) is connected between the air intake of another air outlet of molecular sieve (4) and second under meter (3B), F pipeline (26) is connected between the bottleneck of the air outlet of second under meter (3B) and flask (11), and E pipeline (25) is connected between another bottleneck and second nozzle (7B) of flask (11).
2. the step that adopts atmosphere opening formula MOCVD device as claimed in claim 1 to prepare the adulterated zinc oxide transparent conductive film of aluminium has:
(A) substrate is handled
Choose glass substrate, and be put into successively in acetone (mass percent concentration is 99%), dehydrated alcohol (mass percent concentration is 99%) and the deionized water, remove the dirt of substrate surface respectively behind ultrasonic cleaning cleaning 15min～20min, substrate after will cleaning is then put into the loft drier of 35 ℃～50 ℃ of drying temperatures, behind oven dry 15～20min, take out stand-by;
(B) mould material preparation
With zinc acetylacetonate Zn (C
5H
7O
2)
2H
2O and aluminium acetylacetonate Al (C
5H
7O
2)
3Grind and make the mould material that granularity is 10 μ m～50 μ m, and mould material is placed vaporizer (5);
Zn (the C that adds 9.40g～9.88g in the mould material of consumption: 10g
5H
7O
2)
2H
2Al (the C of O and 0.12g～0.60g
5H
7O
2)
3
(C) preheating of gas channels
C pipeline (23), vaporizer (5), D pipeline (24), E pipeline (25) and chip bench (9) are carried out preheating 5～10min;
(D) logical in advance N
2
When treating that vaporizer (5) temperature rises to 80 ℃～105 ℃, open the master switch on the nitrogengas cylinder (1), low pressure valve is transferred to 0.3MPa～0.5MPa;
Open first on the A pipeline (21) then by air valve (2A), respectively with the flow rate regulation of first flow meter (3A) and the second under meter 3B to 0.3L/min～0.4L/min, make the foreign gas eliminating in the gas channels;
(E) treat that vaporizer (5) temperature reaches 105 ℃～115 ℃, substrate temperature and reaches 170 ℃～270 ℃ and the interior medium temperature of flask (11) and reach 80 ℃～100 ℃, and guarantee that each parameter after 15min is with interior maintenance balance and stability state, closes first flow meter (3A) and second under meter (3B);
The substrate that to dry cleaning then is installed on the chip bench (9);
(F) open first flow meter (3A) and second under meter (3B) once more, and the flow velocity of regulating first flow meter (3A) is 0.6L/min～1.2L/min, the flow velocity of second under meter (3B) is 0.1L/min～0.4L/min; Set depositing time 120min, vapour deposition begins;
(G) behind the vapour deposition result, stop heating successively, stop logical nitrogen at last, thereby make the adulterated zinc oxide transparent conductive film of aluminium preheating zone, insulation belt and vaporizer.
3. employing atmosphere opening formula MOCVD device according to claim 2 prepares the method for the adulterated zinc oxide transparent conductive film of aluminium, and it is characterized in that: the diameter of the aluminum-doped zinc oxide transparent conductive film that makes is 100nm～150nm.
4. employing atmosphere opening formula MOCVD device according to claim 2 prepares the method for the adulterated zinc oxide transparent conductive film of aluminium, and it is characterized in that: the aluminum-doped zinc oxide transparent conductive film that makes can reach more than 90% at the average transmittances of visible region.
5. employing atmosphere opening formula MOCVD device according to claim 2 prepares the method for the adulterated zinc oxide transparent conductive film of aluminium, it is characterized in that: the square resistance of the aluminum-doped zinc oxide transparent conductive film that makes is 24 Ω～440 Ω.
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| GB2512069A (en) * | 2013-03-19 | 2014-09-24 | Pilkington Group Ltd | Aluminium doped tin oxide coatings |
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