CN100357486C - Process for preparing film material by unbalanced normal positional mixing - Google Patents
Process for preparing film material by unbalanced normal positional mixing Download PDFInfo
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- CN100357486C CN100357486C CNB2005101102569A CN200510110256A CN100357486C CN 100357486 C CN100357486 C CN 100357486C CN B2005101102569 A CNB2005101102569 A CN B2005101102569A CN 200510110256 A CN200510110256 A CN 200510110256A CN 100357486 C CN100357486 C CN 100357486C
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Abstract
The present invention relates to a novel method for preparing a doped film by non-equilibrium original-position doping. A pulse laser beam is ablated to be used as a source material target of film substrate, and the other pulse laser beam is ablated to be used as a source material target of doping elements while substrate film layers are deposited by a pulse laser deposition method; impurity elements are uniformly doped into the substrate film layers in the process of deposition and growth, namely that the film deposition and the original-position doping are carried out by a method of double laser beam and double target co-ablation; thus, uniform doping is achieved; the kinds and the parameters of the two laser beams can be respectively adjusted, and the doping density is easy to control; as the film deposition and doping method of non thermodynamic equilibrium, the present invention can break through the restriction of chemical thermodynamics for the doping density to realize heavy doping.
Description
Technical field
The present invention a kind ofly carries out in-situ doped novel method to thin-film material, this method utilize pulse laser beam to the ablation of solid material, carry out with pulse laser sediment method the matrix rete sedimentary simultaneously rete is carried out non-equilibrium in-situ doped.
Background technology
Thin-film material with specific function is the basis that makes advanced components and parts, and the function film of excellent performance depends on advanced film preparing technology.The preparation of many function films or the making of components and parts need be mixed certain density other element toward contact in substrate material, and effective controlled doping concentration and uniform doping are successfully to prepare material and make one of key of components and parts, and doping content is subjected to the restriction of material solid solubility usually again.
Present main adulterating method has in-situ doped in doping after the thin film deposition and the film deposition process.The former is as thermodiffusion doping and ion implantation doping, and the in-situ doped of the latter then carries out under the thermodynamic(al)equilibrium condition.Although these adulterating methods all have one's own knack, but all there is certain limitation, as: the thermodiffusion doping depth is limited and inhomogeneous, also need carry out under hot conditions, and long pyroprocessing may cause the thermal damage of material, causes its hypofunction and performance to reduce; Ion implantation doping causes the damage of substrate material easily, and is difficult to reach even doping at the different depths of material; The in-situ doped restriction that then is subjected to the material solid solubility of thermodynamic(al)equilibrium often is difficult to realize high-concentration dopant.
Summary of the invention
The objective of the invention is to obtain a kind of non-equilibrium in-situ doped method that under normal temperature condition, in the deposition process of thin-film material, can evenly mix, make things convenient for controlled doping concentration.
Utilize pulse laser beam can carry out the pulsed laser deposition of thin-film material to the ablation evaporation of source material.Pulsed laser deposition is existing successful Application aspect film preparation, and almost solid-state the and liquid material of any kind of can be as source material, also may form to be difficult to the thing phase and the structure that form under the normal condition.The present invention is technical foundation with the pulsed laser deposition, adds needed impurity component at the film of depositing of thin film process in growth and carries out in-situ doped.
The preparation method of a kind of film material by unbalanced normal positional mixing that the present invention proposes, be to ablate respectively as the source material target of rete matrix and doped element with two bundle of pulsed laser, implement in-situ doped to rete when carrying out thin film deposition with pulse laser sediment method, wherein mix pulse laser and thin film deposition pulse laser repetition rate are than being 0.02-0.1.
1 pair of embodiments of the present invention is further described below in conjunction with the accompanying drawings: 1) in vacuum or certain background atmosphere, cause the laser-(produced)plasma that the target material (being called for short the ablation product) that produces by ablating forms with a pulse laser beam corresponding source material target of ablating; 2) laser-(produced)plasma expand into substrate place ablation product and forms rete at substrate surface, and this is the matrix rete; 3) another pulse laser beam another source material target of ablating, consequent ablation product transports as impurity atoms and in-situ doped matrix rete in deposition growing to substrate.Two targets are separately fixed in the film forming chamber on two rotary target platforms, uniform rotation in laser ablation process; The substrate rotation that also remains a constant speed in the film process is to obtain uniform rete.
The energy of used laser apparatus is generally the 30-120mJ/ pulse, and energy is big generally speaking, and the rete time of deposition same thickness is short, on the contrary then the time long, identical with the prior art rule.When preparation contains the film of gaseous state element or doping and contains the gaseous state elemental substance, add the gas of an amount of this gaseous substance in the working gas, to remedy the loss of gaseous substance in deposition or the doping process, this is also identical with the prior art rule.
Among the present invention, the vacuum tightness of system is 10
-1-10
-6Pa.
The present invention proposes the device that a kind of non-equilibrium in-situ doped method prepares thin-film material, form by laser aid, lens, source material target, film forming chamber, substrate, wherein, be 90 ° source material target 1,2 about in the film forming chamber 10 being, substrate 7 is in source material target 1, the 2 intermediary plasmas district 8 that overlaps; Produce laser aid 3 ', 4 ' difference corresponding lens 6, window 9 and the source material target 1,2 of pulse laser beam, the target platform of stationary source material target and the specimen holder of substrate are that the magnetic force coupled transmission mechanism is by the outer motor control of film forming chamber.
The present invention is a kind of non-equilibrium material preparation method of chemical heat equilibrated that departs from, and the impurity atoms that is produced by pulse laser ablation has higher energy and activity before the doped matrix rete, can break through the restriction of chemical thermodynamics, obtain thing phase and structure that ordinary method is difficult to obtain, and can realize high-concentration dopant.Impurity atoms is that original position is mixed wherein in the deposition growing process of matrix rete in the inventive method, can obtain even doping film material.There are a plurality of parameters can supply to adjust in present method to adapt to concrete requirement, particularly ablate two source material targets, be used for the matrix film deposition and provide the energy density of two laser of impurity atoms and repetition rate can independent regulation, therefore controlled doping concentration easily.
Description of drawings
Fig. 1 is a device synoptic diagram of implementing the inventive method.
Among the above-mentioned figure, the 1st, the source material target of matrix rete, the 2nd, the source material target of impurity atoms, the 3rd, the pulse laser beam of ablation matrix rete source material target, the 4th, the pulse laser beam of ablation impurity atoms source material target, 3 ', 4 ' is respectively the laser aid of corresponding laser beam, 5 and 6 is lens, the 7th, and substrate, the 8th, the two laser ablation product that ablation is produced to two targets and the laser-(produced)plasma of formation, the 9th, laser beam window, the 10th, film forming chamber.Wherein, all in film forming chamber, the ablation product of target 1 is at substrate surface formation of deposits matrix rete for two source material targets, substrate and laser-(produced)plasmas, and the ablation product of target 2 provides impurity atoms to the matrix rete; Fix the target platform of two source material targets and the specimen holder of substrate and can do uniform rotation by outer motor (the not drawing in the drawings) control of film forming chamber by the magnetic force coupled transmission mechanism.
Embodiment
The present invention has prepared the doping film of multiple different concns with following method.
Embodiment one. the preparation of cobalt doping zinc-oxide (ZnO:Co) film
Press Fig. 1 device, 1 ZnO ceramic target as depositing zinc oxide (ZnO) substrate source material, 2 is impurity source cobalt (Co) metallic target, 3 and 4 is two double frequency pulse laser beams of transferring the output of Q Nd:YAG laser apparatus, Wavelength of Laser all is that 532nm, pulsewidth degree are 5ns, and 3 repetition rate is 10Hz, and 4 repetition rate is 1Hz, 5 and 6 all is that focal length is the 25cm spherical lens, and substrate 7 is the signle crystal alumina (Al of polishing
2O
3).Film forming chamber is evacuated to base vacuum (1 * 10
-1Pa) after, the high purity oxygen gas that charges into air pressure and be 10Pa is as working gas and make gas be in stable flow state, and the electric machine control outer by film forming chamber makes the rotating speed uniform rotation with the tens of commentaries on classics of per minute of target 1, target 2 and substrate 3.Then, open two laser apparatus and carry out the preparation of ZnO:Co film, wherein the ablation product that ablation produced of 1 pair of ZnO target of laser beam forms zno-based plasma membrane layer at substrate deposition, and the zno-based plasma membrane layer of the ablation product that ablation produced of 2 pairs of Co targets of laser beam in deposition growing provides Co atom and in-situ doped in zno-based plasma membrane layer.Prepare that to obtain thickness after 60 minutes be that 0.2 μ m, Co concentration are 1% and the cobalt doping zinc-oxide film of distributed components.The repetition rate that changes laser beam 4 can change the adulterated concentration of Co, and the concentration of Co is proportional to the repetition rate of laser beam 4 basically under the situation of other parameter constant.
Embodiment two. the preparation of aluminium, nitrogen co-doped zinc oxide (ZnO:AlN) film
Device and preparation parameter are basic identical with embodiment one, are that to be evacuated to base vacuum be (1 * 10 to film forming chamber
-5Pa), 2 are changed to aluminium nitride (AlN) ceramic target, and 3 repetition rate is 10Hz, and 4 repetition rate is 0.5Hz, prepare to obtain aluminium, the nitrogen two element codoped zinc-oxide films that thickness is 0.2 μ m after 60 minutes, and wherein aluminium and nitrogen concentration are respectively 0.4% and 0.5%.Equally, can adjust A1 and the adulterated concentration of N, can also in the high purity oxygen working gas, add an amount of high pure nitrogen, prepare Al and N doping content than different aluminium, nitrogen co-doped zinc-oxide film by the repetition rate that changes laser beam 4.
Embodiment three. the preparation of erbium doped silicon (Si:Er) film
Press Fig. 1 configuration, 1 is the Si target as depositing silicon (Si) substrate source material, 2 is impurity source erbium (Er) metallic target, 3 and 4 is two double frequency pulse laser beams of transferring the output of Q Nd:YAG laser apparatus, Wavelength of Laser all is that 532nm, pulse width are 5ns, and 3 repetition rate is 10Hz, and 4 repetition rate is 1Hz, 5 and 6 all is spherical lens, and substrate 7 is the silicon single crystal of polishing.Film forming chamber is evacuated to base vacuum (5 * 10
-4～5 * 10
-6Pa), make target 1, target 2 and claim the rotating speed uniform rotation of the end 3 by the outer electric machine control of film forming chamber with the tens of commentaries on classics of per minute.Then, open two laser apparatus and carry out the preparation of Si:Er film, wherein the ablation product that ablation produced of 1 pair of Si target of laser beam forms Si matrix rete at substrate deposition, and the Si matrix rete of the ablation product that ablation produced of 2 pairs of Er targets of laser beam in deposition growing provides Er atom and in-situ doped in Si matrix rete.Prepared 1～60 minute, and obtained thickness and be 0.05～3 μ m, Er concentration and be 10% and the erbium doped silicon film of distributed components.Wherein, the repetition rate of the laser beam 3 of ablation Si target is fixed as 10Hz, the repetition rate that changes laser beam 4 can change the adulterated concentration of Er, the concentration of Er is proportional to the repetition rate of laser beam 4 basically under the situation of other parameter constant, when the repetition rate of the laser beam 4 of ablation Er target during in 0.1～1Hz range, obtaining Er concentration is 1～10%.Also can use the laser of other wavelength and other pulse width.
Claims (3)
1, a kind of preparation method of film material by unbalanced normal positional mixing, it is characterized in that ablating respectively as the source material target of rete matrix and doped element with two bundle of pulsed laser, implement in-situ doped to rete when carrying out thin film deposition with pulse laser sediment method in film forming chamber (10), wherein mix pulse laser and thin film deposition pulse laser repetition rate are than being 0.02-0.1.
2, according to the described preparation method of claim 1, the vacuum tightness that it is characterized in that system is 10-1
-10
-6Pa.
3, according to the described preparation method of claim 1, it is characterized in that being 90 ° about source material target (1,2) is in film forming chamber (10), there is substrate (7) in source material target (1,2) intermediary plasma overlapping district (8), produce laser aid (3 ', 4 ') difference corresponding lens (6), window (9) and the source material target (1,2) of pulse laser beam, the target platform of stationary source material target and the specimen holder of substrate are that the magnetic force coupled transmission mechanism is by the outer motor control of film forming chamber.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101102569A CN100357486C (en) | 2005-11-10 | 2005-11-10 | Process for preparing film material by unbalanced normal positional mixing |
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| CNB2005101102569A CN100357486C (en) | 2005-11-10 | 2005-11-10 | Process for preparing film material by unbalanced normal positional mixing |
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|---|---|
| CN1793418A CN1793418A (en) | 2006-06-28 |
| CN100357486C true CN100357486C (en) | 2007-12-26 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317155A (en) * | 1998-08-03 | 2001-10-10 | 密苏里大学 | Zinc oxide films containing P-type dopant and process for preparing same |
| CN1372307A (en) * | 2001-02-27 | 2002-10-02 | 连威磊晶科技股份有限公司 | Activation method for reducing p type film resistance by laser |
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2005
- 2005-11-10 CN CNB2005101102569A patent/CN100357486C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317155A (en) * | 1998-08-03 | 2001-10-10 | 密苏里大学 | Zinc oxide films containing P-type dopant and process for preparing same |
| CN1372307A (en) * | 2001-02-27 | 2002-10-02 | 连威磊晶科技股份有限公司 | Activation method for reducing p type film resistance by laser |
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| CN1793418A (en) | 2006-06-28 |
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