Reduce method and the chemical vapor depsotition equipment of impurity particle in reaction chamber
Technical field
The present invention relates to technical field of semiconductors, particularly a kind ofly reduce the method for impurity particle in reaction chamber and a kind of chemical vapor depsotition equipment.
Background technology
Chemical vapor deposition (CVD) is the technology being used for depositing multiple materials be most widely used in semi-conductor industry, comprises most insulating material, most metals material and metal alloy compositions.This technique generally comprises following process: gas reactant arrives substrate surface by convection current and diffusion; Substrate surface adsorption gas molecule, and react, film former and gaseous by-product; Gaseous by-product desorb also leaves substrate surface, leaves reaction chamber by gas barrier.Wherein MOCVD (MOCVD) technology as compound semiconductor materials research and produce means, its high quality, stability, repeatability and scale turn to industry and valued.In the manufacture of super large-scale integration, it is mainly used to depositing titanium nitride, fills the blocking layer of bolt as tungsten.
Due in the forming process of CVD film, there is the processes such as thermolysis and can form by product, and this process need carries out in reaction chamber, make described by product can form impurity particle in cavity, usual impurity can be present in the film of formation, especially for metallic membrane, as titanium nitride, foreign matter content wherein obviously can produce detrimentally affect to its characteristic, thus affects the performance of device in whole unicircuit.
More methods about vapour deposition, please refer to the open file of US Patent No. 20110086496A1.
Summary of the invention
The problem that the present invention solves is to provide and a kind ofly reduces the method for impurity particle in reaction chamber and a kind of chemical vapor depsotition equipment, the method of described minimizing reaction chamber impurity particle effectively can reduce the impurity particle content in reaction chamber, described chemical vapor depsotition equipment utilizes the method for described minimizing reaction cavity impurity particle, impurity can be formed few, the chemical vapour deposition film that quality is high.
For solving the problem, the invention provides a kind of method reducing impurity particle in reaction chamber, comprising: reaction chamber is provided; There is provided and replace substrate in described reaction chamber; On described replacement substrate and reaction chamber inwall formed tectum, the impurity particle in described tectum energy absorption reaction chamber.
Preferably, described reaction chamber is the reaction chamber of chemical vapor deposition method.
Preferably, forming described tectal technique is chemical vapour deposition.
Preferably, the reactant in described chemical vapor deposition method is four dimethyl amine titaniums, trimethyl-gallium, praseodynium iridium or diacetyl acetone platinum.
Preferably, before adopting chemical vapor deposition method formation tectum, place and replace on the heating platform of substrate in reaction chamber.
Preferably, forming described tectal temperature range is 350 DEG C ~ 400 DEG C, and pressure range is that 1 holder ~ 5 are held in the palm, and the reaction times is 0 ~ 300 second.
Preferably, described tectum contains organic composition, and described organic composition has polar covalent bond, the impurity particle in energy absorption reaction chamber.
Preferably, described tectum contains C, H element, forms C-H polar covalent bond.
Preferably, the described tectal thickness of formation is
Technical scheme of the present invention also provides a kind of chemical vapor depsotition equipment, comprises reaction chamber, and described reaction chamber inwall has tectum, the impurity particle in described tectum energy absorption reaction chamber.
Preferably, described reaction chamber is the reaction chamber of chemical vapor deposition method.
Preferably, described tectum adopts chemical vapor deposition method to be formed.
Preferably, the reactant in described chemical vapor deposition method comprises four dimethyl amine titaniums, trimethyl-gallium, praseodynium iridium or diacetyl acetone platinum.
Preferably, the temperature range of described chemical vapor deposition method is 350 DEG C ~ 400 DEG C, and pressure range is that 1 holder ~ 5 are held in the palm, and the reaction times is 0 ~ 300 second.
Preferably, described tectum contains organic composition, and described organic composition has polar covalent bond, the impurity particle in energy absorption reaction chamber.
Preferably, described tectum contains C, H element, forms C-H polar covalent bond.
Preferably, described tectal thickness is
Compared with prior art, the present invention has the following advantages:
By chemical vapor deposition method before substrate forms film, tectum is formed at the inwall of reaction chamber, described tectum is rich in organic composition, and the C in described organic component, the elements such as H, impurity formation covalent linkage is by impurity absorption easily and in chamber, thus effectively can absorb follow-up by-product impurities of carrying out being formed in chemical vapor deposition processes in cavity, described impurity decomposes the by product produced in the by product of generation or other treating processess in thermal process reactor from reactant, thus effectively reduce the content of the impurity particle in reaction process in reaction chamber, reduce the defects such as the granule foreign of the film surface that chemical vapor deposition method is formed, improve the quality of the film formed.
Further, because existing chemical vapor deposition (CVD) equipment carries out not making clean to reaction chamber in CVD reaction process, assembly in cavity can have certain adsorptive power to impurity such as the by products produced in reaction process, but this adsorptive power significantly declines along with the increase of frequency of depositing, in the film formed, foreign matter content then can improve gradually, affects the quality of film.Until maintain CVD equipment, change apparatus assembly and this adsorptive power just can be made to be restored.In order to obtain high-quality deposit film, just needing to maintain equipment frequently, changing apparatus assembly, this is very large for sedimentation effect impact.And be formed with this tectal CVD equipment, impurity absorption ability in chamber is obviously strengthened, thus the frequency of corrective maintenance can be reduced, improve the production efficiency of equipment.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that film surface has impurity particle;
Fig. 2 be the embodiment of the present invention minimizing reaction chamber in the schematic flow sheet of method of impurity particle;
Fig. 3 is the chemical vapor depsotition equipment schematic diagram that embodiments of the invention adopt;
Fig. 4 is that embodiments of the invention form tectal schematic diagram at the reaction chamber inwall of chemical vapor depsotition equipment;
Fig. 5 to Fig. 7 is that the present invention forms the diagrammatic cross-section of TiAlN thin film at substrate surface;
Fig. 8 is formed before and after tectum at reaction chamber inwall, the content of the granule foreign in reaction chamber.
Fig. 9 is formed before and after tectum at reaction chamber inwall, the content of the TiAlN thin film endoparticle impurity formed in reaction chamber.
Figure 10 is the variation diagram along with foreign matter content in time variations reaction chamber.
Embodiment
As described in the background art, the film that chemical vapor deposition (CVD) method is formed can adsorb some impurity particles, surface meeting existing defects (please refer to Fig. 1), and the formation of impurity particle can exert an adverse impact to the quality of film.For example there is as in the TiAlN thin film as tungsten filling bolt blocking layer the performance that impurity particle can have influence on device in whole unicircuit.
Research finds, reactant thermolysis is formed required compound and some by products by chemical vapour deposition technique at a certain temperature, and whole reaction is formed in a reaction chamber, described by product to be easy in follow-up reaction process by thin film adsorbs or to be deposited on film surface, form impurity particle, and then affect the quality of film.
For solving the problem, technical scheme of the present invention proposes a kind of method reducing impurity particle in reaction chamber and the chemical vapor depsotition equipment adopting the method, utilize the method for chemical vapour deposition, tectum is formed at reaction chamber inwall, effectively can absorb the follow-up impurity carrying out in chemical deposition process in cavity to substrate, reduce impurity by the possibility of thin film adsorbs, thus improve the quality of the film formed on substrate.
Below in conjunction with accompanying drawing, by specific embodiment, carry out clear, complete description to technical scheme of the present invention, obviously, described embodiment is only a part for embodiment of the present invention, instead of they are whole.According to these embodiments, those of ordinary skill in the art's obtainable other embodiments all under without the need to the prerequisite of creative work, all belong to protection scope of the present invention.
Please refer to Fig. 2, the implementation step of the embodiment of the present invention, comprising:
S101: chemical vapor depsotition equipment is provided;
S102: provide and replace substrate in heating platform, pass into reactant gases, form tectum at reaction chamber inwall.
Please refer to Fig. 3, chemical vapor depsotition equipment is provided, clean and foresee steps are carried out to the reaction chamber of this conversion unit.
Concrete, the present embodiment adopts CVD equipment, and described CVD equipment comprises: inlet mouth 101, shower nozzle 102, reaction chamber 103, air outlet 104, heating platform 105 and elevating lever 106.
Concrete, the external reacting gas source of described inlet mouth 101, reactant gases is entered in reaction chamber by inlet mouth 101.Shower nozzle 102 is seedpod of the lotus shape, it has the arrangement of multiple hole, evenly enters reaction chamber 103 to make reaction gas physical efficiency.
Heating platform 105 in reaction chamber 103 is resistive heating device, is used for heating the substrate being positioned over its surface in deposition process.In other embodiments of the invention, described heating platform also can be the heating unit of other types, such as radio frequency heating apparatus.Elevating lever 106 connects heating platform 105, for regulating the height of heating platform 105, adjusts the distance of shower nozzle to heating platform 105 surface with this.
Reaction chamber 103 also has venting port 104, and described venting port 104 connects extraneous gas barrier, the foreign gas in reaction chamber 103 is discharged, and keeps the cleaning in reaction chamber 103.
Please refer to Fig. 4, provide and replace substrate 200 in heating platform 105, pass into reactant gases, form tectum 300 at reaction chamber inwall.
Before reaction chamber inwall forms tectum 300, provide described replacement substrate 200 in heating platform, form tectum described in tectum 300 process at reaction chamber inwall and only can be formed at reaction chamber inwall and replace on substrate, thus keep the cleaning of heating platform 105.Follow-up when forming CVD film on substrate, remove described replacement substrate, place substrate in heating platform, ensure that the follow-up quality of forming film forming CVD film on substrate.Put into after replacing substrate in cavity 103, by inlet chamber, discharge the impurity that may exist in reaction chamber 103, and regulate cavity internal gas pressure to 1 to hold in the palm ~ 5 holders.Heated substrate by heating platform afterwards, being adjusted to temperature range is 350 DEG C ~ 400 DEG C.
In the present embodiment, adopt Ti [N (CH
3)
2]
4as reactant gases, by He as carrier gas, entered in reaction chamber 103 by inlet mouth 101 and shower nozzle 102.In other embodiments, carrier gas can be comprise N
2, one or more gas in Ar, He or Ne.Described carrier gas is diluted reactant gases, ensures its homogeneity.Because shower nozzle 102 has multiple air outlet, reactant gases can be made evenly to enter in reaction chamber 103.
Ti [N (CH
3)
2]
4enter after in reaction chamber, decomposes, generate the TiN containing C, H impurity and other by products, reaction formula is as follows:
Ti [N (CH
3)
2]
4→ TiN (C, H)+HN (CH
3)
2+ other hydrocarbons
Wherein, TiN (C, H) can be deposited on and replace substrate 200 surface and reaction chamber 103 inwall formation tectum 300, and other materials are then discharged reaction chamber 103 by gas barrier.The tectal range of reaction temperature of described formation is 350 DEG C ~ 400 DEG C, and pressure range is 1 ~ 5 holder, and the reaction times is 0 ~ 300 second.Under described reaction conditions, the described tectum 300 of formation is unbodied TiAlN thin film, and wherein also comprise the organic composition of a large amount of carbons and protium composition, described tectum 300 thickness is
form the c h bond of polarity between described C and H, the impurity in easy absorption reaction chamber, comprise the HN (CH that in CVD reaction process, thermolysis produces
3)
2with other hydrocarbons, the content of the impurity particle in the CVD film of formation effectively can be reduced.
In other embodiments of the invention, the reactant forming described tectum 300 also can be other organic compound, comprise four dimethyl amine titaniums, trimethyl-gallium, praseodynium iridium or diacetyl acetone platinum etc., the thermolysis in chemical deposition process of described compound, tectum is formed at reaction chamber inwall, described tectum contains the organic elements such as C, H, N, polar covalent bond is formed between described organic element, the impurity in reaction chamber in CVD process can be inhaled, reduce the foreign matter content in CVD film.
After formation tectum, remove replacement substrate, heating platform places substrate, form TiAlN thin film over the substrate.
Please refer to Fig. 5, substrate 400 is provided.
Described substrate material can be the semiconductor materials such as silicon, gallium arsenide or SiGe, also can be the substrate at surface deposition film of the substrate (comprising a part for unicircuit and other elements) of partially disposed or other needs.
Described substrate is put into reaction chamber 103(as shown in Figure 4) heating platform 105(as shown in Figure 4) on, in cavity, set up the reaction atmospheres such as stable temperature, air-flow and air pressure, wherein temperature range is 350 DEG C ~ 400 DEG C, cavity internal gas pressure to 1 holder ~ 5 holder.Ti [N (CH is adopted in the present embodiment
3)
2]
4as reactant gases, by He as carrier gas, enter in reaction chamber 103 by inlet mouth 101 and shower nozzle 102, be sprayed at substrate 400 surface uniformly.At the titanium nitride the first film 401 of substrate surface formation of deposits carbon containing and hydrogen impurity after reactant decomposes, please refer to Fig. 6.In deposition process, reactant decomposes the hydrocarbon organism of part produced can be coated to cap rock 300(as shown in Figure 4) absorb, reduce the content of impurity in reaction chamber 103.
Please refer to Fig. 7, Cement Composite Treated by Plasma is carried out to described the first film, form the second film 402.
The described TiN the first film 401(formed is as shown in Figure 6) be still amorphous structure, and inside has C, H element.Remove the C of described the first film inside by Cement Composite Treated by Plasma, organic composition that H element is formed, form pure TiN second film 402.
In prior art, carry out not making clean to reaction chamber in CVD reaction process, cavity components has certain physical adsorption ability to impurity such as the by products produced in reaction process, but this adsorptive power significantly declines along with the increase of frequency of depositing, in the film formed, foreign matter content then can improve gradually, affects the quality of film.Until maintain CVD equipment, change cavity components and this adsorptive power just can be made to be restored.In order to obtain high-quality deposit film, just needing to maintain equipment frequently, changing cavity components, this is very large for sedimentation effect impact.In embodiments of the invention, before substrate surface forms TiAlN thin film, first form the tectum containing organic compositions such as C, H of amorphous structure at reaction chamber inwall, organic composition wherein has polar covalent bond, the impurity in easy absorption reaction chamber.The described tectum containing organic composition has higher adsorptive power for impurity particle, described tectum covers reaction chamber inner chamber body assembly surface, effectively can improve reaction chamber inwall cavity components to the adsorptive power of the impure by-products produced in reaction process, reduce the foreign matter content in reaction chamber, thus formed on substrate in the process of TiAlN thin film, be not easy to form particulate state at film surface to pollute, effectively improve the quality of TiAlN thin film, reduce the resistance of TiAlN thin film, improve the performance of the integrated circuit (IC)-components of follow-up formation.For the enhancing of impurity absorption ability in chamber, the frequency of corrective maintenance can be reduced, improve the production efficiency of equipment.
Please refer to Fig. 8, Fig. 8 is formed before and after tectum at reaction chamber inwall, the content of the granule foreign in reaction chamber.
Concrete, after the completion of reaction, after He gas is passed into reaction chamber, measure the content of granule foreign in the He gas of discharging.Can obviously find out, and do not formed compared with tectum, after reaction chamber inwall forms tectum, the content of reaction chamber endoparticle impurity obviously declines, and is close to 0.This shows that tectum has very strong adsorptive power for impurity.In other embodiments of the invention, the gas passed into can be N
2, one or more gases in He, Ar or Ne.
Please refer to Fig. 9, Fig. 9 is formed before and after tectum at reaction chamber inwall, the content of the TiAlN thin film endoparticle impurity formed in described reaction chamber.
Concrete, reactant is passed in reaction chamber, in formation of deposits TiAlN thin film process, measure the granule foreign content of deposit film.With do not formed compared with tectum, after reaction chamber inwall forms tectum, the content of described TiAlN thin film endoparticle impurity obviously declines.
Please refer to Figure 10, within front ten days, inner reaction cavity wall does not form tectum, in deposited on substrates TiAlN thin film and to cavity impurity particle carry out deterioration process.Along with number of days increases, in the TiAlN thin film of formation, the content of impurity particle increases gradually, shows that the adsorptive power of reaction chamber inner assembly to impurity declines gradually along with the increase of frequency of depositing.At the 11 day, tectum is formed at reaction chamber inwall, carry out the deposition of TiAlN thin film again, find that the content of impurity particle in the TiAlN thin film now formed significantly declines, show that the tectum formed at reaction chamber inwall in technical scheme of the present invention can improve the adsorptive power to impurity in cavity significantly, reduce the content of impurity in deposit film.
Embodiments of the invention form tectum at reaction chamber inwall, utilize the adsorptive power of organic composition raising to impurity in reaction chamber in tectum.On the one hand, improve the quality of formed film; On the other hand, improve wafer quantity and good article rate that described CVD equipment can deposit within a maintenance period, effectively improve the production efficiency of board.And the present embodiment also utilizes CVD method to form TiAlN thin film in the described tectal reaction chamber of formation, and test the impurity particle content in this process in reaction chamber, result shows, the method effectively can reduce the impurity particle in reaction chamber.
In other embodiments of the invention, the chemical vapour deposition carried out in described reaction chamber can also comprise other chemical deposition process or other chemical vapor deposition methods etc. based on pyrolysis.The reaction chamber inwall that can carry out in described technique forms the tectum containing organic composition, in described organic composition, there is polar covalent bond, to impurity in chamber, there is adsorptive power, improve reaction chamber intraware to the adsorptive power of the impurity produced in reaction process, improve the quality of the final CVD film formed.
Embodiments of the invention additionally provide a kind of chemical vapor depsotition equipment, comprise reaction chamber, and described reaction chamber inwall has tectum, the impurity in described tectum energy absorption reaction chamber.
Concrete described tectum adopts the method for impurity particle in above-mentioned minimizing reaction chamber to be formed.Described tectum uniform fold is at the internal surface of reaction chamber, and thickness is
described tectum is rich in organic composition, and described organic composition comprises C, H or N element, and there is in described organic composition polar covalent bond can impurity particle in active adsorption reaction chamber, improve the quality of forming film of this chemical vapor depsotition equipment.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Any those of ordinary skill in the art, do not departing under technical solution of the present invention ambit, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belongs in the scope of technical solution of the present invention protection.