CN101768728A - Method for preparing doped ZnO-based film through magnetron sputtering - Google Patents

Method for preparing doped ZnO-based film through magnetron sputtering Download PDF

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CN101768728A
CN101768728A CN201010042779A CN201010042779A CN101768728A CN 101768728 A CN101768728 A CN 101768728A CN 201010042779 A CN201010042779 A CN 201010042779A CN 201010042779 A CN201010042779 A CN 201010042779A CN 101768728 A CN101768728 A CN 101768728A
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zno
doped
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sputtering
based film
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马晓翠
吕有明
柳文军
曹培江
朱德亮
贾芳
黄保
李清华
盛国浩
叶家聪
向恢复
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Shenzhen University
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Abstract

The invention provides a method for doping and growing ZnO-based film through magnetron sputtering. The method comprises the following steps: placing a substrate in the reaction chamber of a magnetron sputtering device, vacuumizing the reaction chamber to lower than 1*10<-4>Pa; separately placing ZnO target and doped source element target on the radio frequency target position and DC or electromagnetic target position of the turntable of the reaction chamber, introducing oxygen and argon, which are used as sputtering atmosphere, in a buffer chamber, fully mixing in the buffer chamber, introducing the mixed gas in a vacuum reaction chamber, performing sputtering growth when the pressure is 1-3Pa and the temperature of the substrate is below the room temperature; selecting a sample position and adjusting the sputtering times of the radio frequency target position and DC or electromagnetic target position through a preset program to alternately grow ZnO films and doped element layers; and after the growth placing the doped ZnO-based film in vacuum, air or nitrogen atmosphere to anneal for 30-60 minutes at 400-800 DEG C.

Description

A kind of preparation method of doped ZnO-based film through magnetron sputtering
Technical field
The invention belongs to semi-conductor film material with function technical field, relate in particular to a kind of method of magnetron sputtering doped growing zno-based film.
Background technology
ZnO film is a kind of direct band gap semiconductor material with wide forbidden band, energy gap under the normal temperature is 3.37eV, its exciton bind energy is up to 60meV, have excellent photoelectricity, piezoelectricity and dielectric characteristics, nontoxicity, raw material is easy to get and is cheap, is considered to the laser apparatus luminescent material of the most potential ultraviolet, blue light.The ZnO of intrinsic presents n N-type semiconductorN feature usually, but its carrier concentration is lower, if will obtain sufficiently high carrier concentration, then needs it is mixed.In different doping, representative doping system has: aluminium doping ZnO (Al-doped ZnO, be called for short AZO) film is considered to the best equivalent material of ITO (Sn-doped indium oxide is called for short ITO) film; Transient metal doped ZnO can obtain the diluted magnetic semiconductor that Curie temperature is higher than room temperature; The adulterated MgxZn of Mg 1-xThe O alloy firm has the major application meaning on ultraviolet detection.ZnO film becomes one of research focus of semiconductor optoelectronic functional materials and device gradually in recent years.
Magnetron sputtering plating is one of most popular method of preparation zno-based film.Yet utilize magnetron sputtering technique to prepare sull, still lack effective doping means at present.Generally, the grow film of a certain specific components of sputter needs the corresponding with it sputtering target material of prepared beforehand, if the film of preparation change of component, then need prepare a series of corresponding with it targets, this has not only improved research cost, has also limited the flexible adjustment of film composition simultaneously.This is that sputtering method prepares the difficult problem that film faces.
Summary of the invention
The objective of the invention is to adopt submolecule layering doping techniques, solve the doping problem in the sputter coating process, the adulterated zno-based film of growing and preparing.
The present invention is achieved in that
The principle of submolecule (atom) layer layering doping techniques is: by sputtering time, alternating growth ZnO film and the impurity element layer of computer program control ZnO target and impurity element target (for example: Co, Al and Mg) target.For making impurity uniform distribution in ZnO film, the growth sputtering time of impurity element should be short as much as possible, and the thickness of the discontinuous film that is generated is the submolecule magnitude, so be called submolecule layer layering doping techniques, for making Impurity Distribution even, sample needs usually through The high temperature anneal.
The method of magnetron sputtering doped growing zno-based film provided by the present invention comprises step:
1) respectively ZnO target and doped source element target are placed on reaction chamber radio frequency target position and direct current or electromagnetism target position, position and the distance between the substrate that target is placed are 65-80mm;
2) substrate is placed on sample holder internal fixing after, be sent to the magnetic control sputtering device reaction chamber one by one by the magnetictransmission bar, and be placed in the sample library of rotating disk, reaction chamber is evacuated to pressure and is lower than 1 * 10 -4Pa is a sputtering atmosphere with oxygen and argon gas, with two kinds of gas input buffering chambers, and introduces vacuum reaction chamber behind the surge chamber thorough mixing, is under the room temperature at 1~3Pa pressure, underlayer temperature, carries out the sputter growth;
3) by predefined program, the radio frequency target position is also adjusted and the sputtering time of direct current or electromagnetism target position in selected sample position, with alternating growth ZnO film and doped element layer;
4) behind the growth ending, with the zno-based film of doped growing in vacuum, air or nitrogen atmosphere, 400 ℃-800 ℃ annealing 30-60 minute down.Usually Si and quartz substrate annealing temperature are 800 ℃ of soaking times 30 minutes, and the glass substrate annealing temperature is 400 ℃ of soaking times 60 minutes.After annealing finishes, treat to take out after sample naturally cools to room temperature.
Among the preparation method of above-mentioned magnetron sputtering doped growing zno-based film, in the predefined program of described step 3), satisfy following funtcional relationship between the sputtering time of ZnO and doped element, sedimentation rate, the doping content:
m 1=ρ 1v 1t 1S,
m 2=ρ 2v 2t 2S,
x ( wt % ) = m 2 m 2 + m 1 * 100 % ,
In the formula, m 1m 2Be respectively the deposition of ZnO and doped element, ρ 1, ρ 2Be respectively the density of ZnO and doped element, v 1, v 2Be respectively the sedimentation rate of ZnO and doped element, t 1, t 2Be respectively the sputtering time of ZnO and doped element, S is a Substrate Area, and x is the doping content of doped element.
Among the preparation method of above-mentioned magnetron sputtering doped growing zno-based film, the doped source element target of described step 3) is to be selected from Co target, Al target or Mg target, also can be other as metal or SnO such as Fe, Ni, Cu 2, TiO 2Deng conductor oxidate solid target.
Among the preparation method of above-mentioned magnetron sputtering doped growing zno-based film, position and the distance between the substrate that the ZnO target of described step 3) and doped source element target are placed are 65-80mm.
Among the preparation method of above-mentioned magnetron sputtering doped growing zno-based film, described step 2) oxygen in the sputtering atmosphere and the blending ratio of argon gas are: O 2: [Ar+O 2]=0~0.5.
Among the preparation method of above-mentioned magnetron sputtering doped growing zno-based film, described step 2) general gas flow of oxygen and argon gas is 15~35sccm in the sputtering atmosphere.
Sputtering power during among the preparation method of above-mentioned magnetron sputtering doped growing zno-based film, described step 2) sputter growth is 40~200W.
Among the preparation method of above-mentioned magnetron sputtering doped growing zno-based film, described step 2) sedimentation rate of ZnO is in the sputter process of growth
Figure G2010100427795D00031
The sedimentation rate of doped source element is
Implementing the beneficial effect that technical scheme provided by the present invention has is, it adopts submolecule layer layering doping techniques to prepare doped ZnO-based film, compare with traditional method, it is low that this method has a cost, easy and simple to handle, easy controlled doping amount, characteristics such as uniform doping are for the preparation doped ZnO-based film provides convenient effective means.In addition, this method can be used for the doping of other oxide compounds (or non-oxidized substance) film.
Description of drawings
It shown in Fig. 1-1 XRD spectra of the ZnO film under the different al doping in the one embodiment of the invention;
It shown in Fig. 1-2 the ZnO film transmission spectrum under the different al doping in the one embodiment of the invention;
Shown in Fig. 1-3 ZnO film under the different al doping in the one embodiment of the invention (α hv) 2~h υ spectrogram;
It shown in Fig. 2-1 XRD spectra of the ZnO film under the different Co dopings in the another embodiment of the present invention;
It shown in Fig. 2-2 each atomic percentage conc spectrogram in the ZCO film after 400 ℃ of annealing in the another embodiment of the present invention;
Shown in Fig. 3-1 be among another embodiment of the present invention after 800 ℃ of annealing Mg xZn 1-xThe XRD spectra of O film;
Shown in Fig. 3-2 be among another embodiment of the present invention after 800 ℃ of annealing Mg xZn 1-xThe transmission spectrum of O film;
Shown in Fig. 3-3 be among another embodiment of the present invention after 800 ℃ of annealing Mg xZn 1-xThe energy gap width figure of O film.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
In order more to be expressly understood the present invention in detail, the preparation process of doped ZnO-based film is described in detail below.
(a) ZnO powder is made round pie with tabletting machine, high temperature burns till the ZnO ceramic target;
(b) respectively ZnO ceramic target and doped source element target (Co, Al or Mg etc.) are placed on radio frequency and direct current (or electromagnetism target) target position, substrate is placed on certain distance on the target, about 8 centimetres;
(c) shut bell jar, vacuumize, spatter chamber vacuum tightness as the master and be lower than 1 * 10 -4During Pa, begin growth;
(d) Sheng Chang concrete steps are as follows: take out the Ar feed channel in advance, open the mass flowmeter power supply, regulate the Ar flow and transfer to desirable value, and regulate high vacuum valve and make and mainly spatter chamber vacuum tightness and maintain 2-3Pa.Connect the target water coolant, sputter is controlled all knobs are threaded to zero-bit on the power panel, open sputter Controlling System general supply; Open radio-frequency power supply, after the preheating 5 minutes, open plate and compress switch (the about 50mA of initial current, voltage 200V), adjustable plate is pressed, plate current, resistance dynamometer also should have indication, regulate matching capacitance repeatedly, make reflective power minimum, the target build-up of luminance, adjustable plate is depressed into power demand, and sputtering power is a power input about 80% during general optimum matching; Start the DC direct supply, be adjusted to power demand, doped element target build-up of luminance;
Start pre-set computer rotating disk sequence of control, the position and the plated film time of each sample on the rotating disk are controlled, make sample by the impurity element layer that sets pattern deposition ZnO film and submolecule magnitude thickness.By the sputtering time controlled doping amount of control impurity element, thereby obtain the zno-based film of different dopings; Air pressure is controlled at the 1Pa magnitude in the coating process;
(e) the zno-based film sample of prepared different dopings, the logical need through 400-800 ℃ of The high temperature anneal 30-60 minute, annealing atmosphere can be selected vacuum, air or nitrogen etc.
In process of growth, the cycle of ZnO film and doped element alternating growth is by the shortest sputtering time decision of growth thickness, doping content, sputter rate and the system of ZnO film.For example, growth thickness is
Figure G2010100427795D00051
ZnO film in to mix weight percent be 2% Al element, the sedimentation rate of ZnO is
Figure G2010100427795D00052
The sputtering time of ZnO target is 2000 seconds, and the sedimentation rate of Al is
Figure G2010100427795D00053
Sputtering time is calculated as follows:
The quality of deposit film correspondence: m 1,21,2v 1,2t 1,2S---(1)
[ρ wherein 1Density=5.606g/cm for ZnO 3, ρ 2(density as Al is 2.702g/cm for the density of the density Al of doped element 3), v 1,2Be respectively the sedimentation rate of ZnO and Al layer, S is a Substrate Area]
Doped element weight percent (doping content): x ( wt % ) = m 2 m 2 + m 1 * 100 % - - - ( 2 )
The sputtering time of corresponding A l target was 30s when simultaneous (1), (2) formula can get doping content and be 2 (wt%).
Come the present invention is described in detail with specific embodiment below.
Embodiment 1---and adopt high purity Al target as doped source, growth AZO film on quartz substrate.
At first utilize submolecule layering doping techniques, alternately magnetron sputtering ZnO and Al target prepare Al ZnO thin film doped (AZO), and in air atmosphere, through 400-800 ℃ of The high temperature anneal 30-60 minute.Growth conditions is:
Figure G2010100427795D00061
By changing the sputtering time of Al target, control mix Al content (0~6wt%), prepare good transparent conductive film (TCO).After 400 ℃ of anneal, improved the crystalline quality of film, XRD result shows that all films have only (002) diffraction peak, have tangible C axle preferrel orientation, see Fig. 1-1.In visible-range, the average transmittance of film surpasses 80%, sees Fig. 1-2.By to ellipse inclined to one side spectrographic match, provide optical constant spectrum, the thickness of AZO film sample, and calculate optical parametrics such as uptake factor and energy gap, find in the process of growth, along with mixing increasing of Al content, the energy gap of film moves (blue shift) to the shortwave direction earlier, moves (red shift) to the long wave direction subsequently and sees Fig. 1-3.
Embodiment 2---and adopt high-purity C o as the doped source target, ZnO:Co (ZCO) film of on the Si substrate, growing.
At first utilize submolecule layering doping techniques, alternating sputtering ZnO and Co target, preparation Co ZnO thin film doped (ZCO), and in vacuum atmosphere, through 400-800 ℃ of The high temperature anneal 30-60 minute.Growth conditions is:
Figure G2010100427795D00062
Figure G2010100427795D00071
The XRD test result shows that a very strong diffraction peak all appears in (002) crystal face of the ZCO film of different Co dopings, and their 2 θ and pure ZnO crystal diffraction peak are very approaching, show that all ZCO films all have the c axle preferrel orientation, see Fig. 2-1.Depth spectrum by each atom in the ZCO film of XPS test shows that the layering doping techniques is a kind of effective film doping method, the Co element is higher than inside a little at film surface place content, but the distribution of Co in film still relatively uniformly, seen Fig. 2-2 generally.The ZCO film resiativity descends with the increase of Co doping.In addition, experiment finds that the ferromegnetism of ZCO film strengthened with the increase of doping when the Co doping was low, and the ferromegnetism of film was the strongest when Co content was 4.5% left and right sides.Adopt the elliptically polarized light spectral technology, studied the ellipse polarisation spectrum of film, simulated refractive index n and optical extinction coefficient k with air-film-substrate three layer model, and thus match the energy gap of film, discovery is along with the increase of Co content, and the phenomenon of red shift appears in the optical absorption limit.
Embodiment 3---and adopt high purity Mg target as doped source, Mg grows on quartz substrate xZn 1-xThe O alloy firm.
Alternately magnetron sputtering Mg target and ZnO target have prepared the ZnO thin film doped (Mg of Mg xZn 1-xO), all in nitrogen atmosphere, anneal is 30 minutes under 800 ℃ of high temperature for sample.Growth conditions is:
Figure G2010100427795D00072
Figure G2010100427795D00081
Studies show that: when the Mg component is low, all Mg xZn 1-xAppearance class ZnO (0002) diffraction peak of O film has tangible C axle preferrel orientation, and film is six side's phase structures; When Mg component 〉=50%, except class ZnO (0002) diffraction peak occurring, class MgO (200) diffraction peak has also appearred, and this moment, sample was six a sides phase and the Fig. 3-1 that meets each other of mixing cube mutually; In the visible region, the average transmittance of film surpasses 85%, sees Fig. 3-2.Along with the raising of Mg component, transmissivity slightly descends; When the Mg component was low, the blue shift phenomenon all took place along with the increase of oxygen level, the raising of annealing temperature and the increase of Mg component in ABSORPTION EDGE, and corresponding energy gap width increases gradually; When the Mg component was higher, the ABSORPTION EDGE of film was along with the increase continuation blue shift of Mg component is seen Fig. 3-3.Mg xZn 1-xThe square resistance of O film shows: along with the Mg component increases from 0~70%, square resistance reduces gradually with the film of submolecule layering doping method preparation.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. the preparation method of a magnetron sputtering doped growing zno-based film is characterized in that, comprises step:
1) respectively ZnO target and doped source element target are placed on reaction chamber radio frequency target position and direct current or electromagnetism target position, position and the distance between the substrate that target is placed are 65-80mm;
2) substrate is placed on sample holder internal fixing after, be sent to the magnetic control sputtering device reaction chamber one by one by the magnetictransmission bar, and be placed in the sample library of rotating disk, reaction chamber is evacuated to pressure and is lower than 1 * 10 -4Pa is a sputtering atmosphere with oxygen and argon gas, with two kinds of gas input buffering chambers, and introduces vacuum reaction chamber behind the surge chamber thorough mixing, is under the room temperature at 1~3Pa pressure, underlayer temperature, carries out the sputter growth;
3) by predefined program, the radio frequency target position is also adjusted and the sputtering time of direct current or electromagnetism target position in selected sample position, with alternating growth ZnO film and doped element layer;
4) behind the growth ending, with the zno-based film of doped growing in vacuum, air or nitrogen atmosphere, 400 ℃-800 ℃ annealing 30-60 minute down;
5) after annealing finishes, treat to take out after sample naturally cools to room temperature.
2. the preparation method of magnetron sputtering doped growing zno-based film as claimed in claim 1, it is characterized in that, in the predefined program of described step 3), satisfy following funtcional relationship between the sputtering time of ZnO and doped element, sedimentation rate, the doping content:
m 1=ρ 1v 1t 1S,
m 2=ρ 2V 2t 2S,
x ( wt % ) = m 2 m 2 + m 1 * 100 % ,
In the formula, m 1m 2Be respectively the pairing deposition quality of ZnO and doped element, ρ 1, ρ 2Be respectively the density of ZnO and doped element, v 1, v 2Be respectively the sedimentation rate of ZnO and doped element, t 1, t 2Be respectively the sputtering time of ZnO and doped element, S is a Substrate Area, and x is the doping content of doped element.
3. the preparation method of magnetron sputtering doped growing zno-based film as claimed in claim 1 is characterized in that, doped source element target is to be selected from Co target, Al target or Mg target in the described step 3), or be Fe, Ni, Cu is ferromagnetic or non-ferromagnetic metal or SnO 2, TiO 2Conductor oxidate solid target.
4. the preparation method of magnetron sputtering doped growing zno-based film as claimed in claim 1 is characterized in that, ZnO target and doped source element target are placed in the described step 3) position and the distance between the substrate are 65-80mm.
5. the preparation method of magnetron sputtering doped growing zno-based film as claimed in claim 1 is characterized in that described step 2) in oxygen in the sputtering atmosphere and the blending ratio of argon gas be: O 2: [Ar+O 2]=0~0.5
6. the preparation method of magnetron sputtering doped growing zno-based film as claimed in claim 1 is characterized in that described step 2) in the sputtering atmosphere general gas flow of oxygen and argon gas be 15-35sccm.
7. the preparation method of magnetron sputtering doped growing zno-based film as claimed in claim 1 is characterized in that described step 2) in the sputtering power in sputter when growth be 40~200W.
8. the preparation method of magnetron sputtering doped growing zno-based film as claimed in claim 1 is characterized in that described step 2) in the sputter process of growth sedimentation rate of ZnO be
Figure F2010100427795C00021
The sedimentation rate of doped source element is
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Application publication date: 20100707