CN101570856B - Film formation device - Google Patents
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- CN101570856B CN101570856B CN2009101426299A CN200910142629A CN101570856B CN 101570856 B CN101570856 B CN 101570856B CN 2009101426299 A CN2009101426299 A CN 2009101426299A CN 200910142629 A CN200910142629 A CN 200910142629A CN 101570856 B CN101570856 B CN 101570856B
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Abstract
The present invention relates to a film formation apparatus for a semiconductor process, comprising: a process container; a support member configured to support the target substrate inside the processfield; a heater configured to heat the target substrate inside the process field; an exhaust system configured to exhaust gas inside the process field; a first process gas supply circuit configured t o supply a first process gas for film formation; a second process gas supply circuit configured to supply a second process gas for reacting with the first process gas; a third process gas supply circuit configured to supply a third process gas different from first and second process gases; an exciting mechanism configured to selectively excite the second process gas; and a control section configured to control an operation of the apparatus. The film formation method for a semiconductor process is arranged to form a thin film on a target substrate by CVD.
Description
The application is that the application number that proposed on June 28th, 2005 is 200510080241.2 divides an application
Technical field
The present invention relates on processed substrates such as semiconductor wafer to form film formation device and method that semiconductor processes that film uses is used.At this, so-called semiconductor processes is meant: in order to pass through in wafer or LCD (LCD, Liquid Crystal Display) forms semiconductor layer, insulating barrier, conductive layer etc. with the pattern of regulation or on the processed substrates such as glass substrate of FPD (flat-panel monitor, Flat Panel Display) usefulness and be manufactured on the various processing that the structure that contains semiconductor device or the wiring that is connected with semiconductor device, electrode etc. on this processed substrate is implemented.
Background technology
When making the semiconductor device that constitutes semiconductor integrated circuit,, for example on the semiconductor wafer, various processing such as film forming, oxidation, diffusion, upgrading, annealing, etching have been implemented at processed substrate.The spy opens in the 2004-6801 communique, discloses the method for carrying out these semiconductor processes in vertical (so-called batch (-type)) annealing device.In the method, at first semiconductor wafer is transferred on the vertical chip support from wafer case, and be supported with multistage formation.In wafer case, example goes into to hold 25 wafer, and can load 30～150 wafer on chip support.Then, change chip support over to its inside from the below of container handling, simultaneously container handling is carried out the air-tightness locking.Then, under the state of various treatment conditions such as the flow of control and treatment gas, processing pressure, treatment temperature, the heat treatment of stipulating.
In recent years, be accompanied by, wish in the manufacturing process of semiconductor device, to alleviate its thermo-lag, improve Devices Characteristics semiconductor integrated circuit Highgrade integration and the highly requirement of miniaturization more.In vertical processing unit, wish to require the method for improvement semiconductor processes according to some.For example in the middle of CVD (the Chemical Vapor Deposition chemical vapor deposition) method that a kind of film forming is handled, a kind of one side base feed gas etc. is off and on arranged, one or more layers that carries out on one side atom or molecular level thick layer be the method for film forming (for example, the spy opens flat 6-45256 communique, the spy opens flat 11-87341 communique) repeatedly.Such film build method is commonly referred to as ALD (Atomic layer Deposition atomic layer deposition) method, thus, even wafer is not exposed under the high temperature like this, also can carries out purpose and handle.
Figure 13 is using as the dichlorosilane (DCS) of silane-based gas with as the NH of nitriding gas
3Form under the situation of silicon nitride film (SiN), in film build method in the past, expression supply gas and the timing diagram that applies the RF form.As shown in Figure 13, in container handling, sandwich is cleaned the phase, intermittently mutual DCS and the NH of supplying with
3Gas.Supplying with NH
3Apply RF (high frequency) during gas, promote in container handling, to generate the nitridation reaction of plasma.That is, at first in container handling, supply with DCS, thus, on wafer surface, adsorb one or more layers DCS with molecular level.Remaining DCS is discharged during cleaning.Then, by supplying with NH
3Generate plasma, form silicon nitride film by nitrogenize at low temperatures.Carry out a succession of such operation repeatedly, just finished the film of specific thickness.
In above-mentioned film build method, not only obtain reasonable stepped covering, and compare with the film build method that carries out high temperature CVD, owing to implemented low temperatureization, can reduce the Si-H key in the film, promote membranous characteristic.But in this kind film build method in the past, although promoted reaction to carry out by plasma, film forming speed is still quite low, and productivity ratio is also low.
Summary of the invention
The purpose of this invention is to provide a kind of film build method and film formation device, can keep the high-quality while of film, can improve film forming speed significantly.
A first aspect of the present invention is the film build method that a kind of semiconductor processes is used, this film build method be supply with in holding the processing region of processed substrate that film forming uses first handle gas and with above-mentioned first handle second of gas reaction and handle gas, by CVD film forming method on above-mentioned processed substrate, it is characterized in that, comprise following intersection operation:
To above-mentioned processing region supply with above-mentioned first and second first operations of handling gases,
Stop to above-mentioned processing region supply with above-mentioned first and second second operations of handling gases,
Supply with above-mentioned second when handling gas to above-mentioned processing region, stop to above-mentioned processing region supply with above-mentioned first the 3rd operation of handling gas,
Stop to supply with the 4th operation of the above-mentioned first and second processing gases to above-mentioned processing region.
A second aspect of the present invention is the film build method that a kind of semiconductor processes is used, this film build method be supply with in the processing region that holds processed substrate that film forming uses first handle gas, with above-mentioned first handle second of gas reaction handle gas and with first and second the 3rd any all different processing gases of handling in the gases, by CVD film forming method on above-mentioned processed substrate, it is characterized in that, comprise following intersection operation:
Supplying with the above-mentioned first and the 3rd processing gas to above-mentioned processing region when, stop to supply with first operation of the above-mentioned second processing gas to above-mentioned processing region, above-mentioned first operation has by excitation mechanism, make the above-mentioned the 3rd handle body with excited state supply to above-mentioned processing region during,
Stop to above-mentioned processing region supply with above-mentioned first to the 3rd second operation of handling gas,
Supply with to above-mentioned processing region above-mentioned second handle gas in, stop to above-mentioned processing region supply with the above-mentioned first and the 3rd the 3rd operation of handling gas,
Stop to supply with the 4th operation of first to the 3rd processing gas to above-mentioned processing region.
A third aspect of the present invention is the film formation device that a kind of semiconductor processes is used, and it is characterized in that, comprising:
Have the processing region that holds processed substrate container handling,
In above-mentioned processing region, support above-mentioned processed substrate holding components,
Heat the above-mentioned processed substrate in the above-mentioned processing region heater,
Discharge gas in the above-mentioned processing region gas extraction system,
To above-mentioned processing region supply with film forming with first treating-gas supply system of the first processing gas,
To above-mentioned processing region supply with above-mentioned first handle second of gas reaction handle second treating-gas supply system of gas,
Optionally the above-mentioned processing region of subtend supply with above-mentioned second handle excitation mechanism that gas excites,
The control section of control said apparatus action.
A fourth aspect of the present invention is the medium that comprises that the available computers that contains the program command that moves in processor reads, it is characterized in that,
Supply with in the processing region that holds processed substrate that film forming uses first handle gas and with above-mentioned first handle second of gas reaction and handle gas, in the CVD film formation device that film forming semiconductor processes is used on above-mentioned processed substrate, the said procedure instruction is when being moved by processor, alternatively implement following operation
To above-mentioned processing region supply with above-mentioned first and second first operations of handling gases,
Stop to above-mentioned processing region supply with above-mentioned first and second second operations of handling gases,
Supply with to above-mentioned processing region above-mentioned second handle gas in, stop to above-mentioned processing region supply with above-mentioned first the 3rd operation of handling gas,
Stop to supply with the 4th operation of the above-mentioned first and second processing gases to above-mentioned processing region.
A fifth aspect of the present invention is the medium that comprises the embodied on computer readable of the program command that is used for moving on processor, it is characterized in that,
Supply with in the processing region that holds processed substrate that film forming uses first handle gas, with above-mentioned first handle second of gas reaction handle gas and with first and second any all different the 3rd processing gases of handling in the gases, in the CVD film formation device that film forming semiconductor processes is used on above-mentioned processed substrate, the said procedure instruction is when being moved by processor, alternatively implement following operation
Supplying with the above-mentioned first and the 3rd processing gas to above-mentioned processing region when, stop to supply with first operation of the above-mentioned second processing gas to above-mentioned processing region, above-mentioned first operation has by excitation mechanism, make the above-mentioned the 3rd handle gas with excited state supply to above-mentioned processing region during,
Stop to above-mentioned processing region supply with above-mentioned first to the 3rd second operation of handling gas,
Supply with to above-mentioned processing region above-mentioned second handle gas in, stop to above-mentioned processing region supply with the first and the 3rd the 3rd operation of handling gas,
Stop to supply with the 4th operation of above-mentioned first to the 3rd processing gas to above-mentioned processing region.
In aspect first to the 5th, above-mentioned first handles gas comprises silane-based gas, and above-mentioned second handles gas comprises nitriding gas or nitrogen oxidizing gas, and the above-mentioned the 3rd handles gas comprises the gas that is selected from nitrogen, rare gas, nitrogen oxide gas.For example, the above-mentioned first processing gas comprises from dichlorosilane (DCS), hexachloro-silane (HCD), single silane (SiH
4), disilane (Si
2H
6), more than one the gas selected in the hexamethyldisilazane (HMDS), tetrachloro silicane (TCS), disilazane (DSA), nitrilotrisilane (TSA), dual-tert-butyl amino silane (BTBAS).Above-mentioned second handles gas comprises, for example, is selected from ammonia [NH
3], nitrogen [N
2], nitrous oxide [N
2O], more than one gas of nitric oxide [NO].
Other purposes of the present invention and advantage will be stated in the narration below, and will narrate thus or by implementing a detail knowledge of the present invention part wherein.Objects and advantages of the present invention can be implemented and obtain by means of mode that particularly points out in the back and combination thereof.
Description of drawings
Incorporate the present invention into and constitute the accompanying drawing of this specification part, the preferred embodiments of the present invention are described, and, be used for illustrating principle of the present invention in the above with being described in detail of general narration that provides and preferred embodiment given below.
Fig. 1 is the profile of the film formation device (vertical CVD device) of expression first embodiment of the invention.
Fig. 2 is the cross section plane graph that is illustrated in the part of device shown in Fig. 1.
Fig. 3 is in the film build method of first execution mode, and the timing diagram of RF state is supplied with and applied to expression gas.
The figure of the thickness data of Fig. 4 silicon nitride film that to be expression obtained by the experiment 1 of first execution mode.
Fig. 5 is the figure of expression by the experiment 1 silicon nitride film film forming speed that obtains.
Fig. 6 is the figure of expression by the inner evenness of the experiment 1 silicon nitride film thickness that obtains.
Fig. 7 is the infrared ray diffraction result schematic diagram of expression by experiment 1 silicon nitride film that obtains.
Fig. 8 is in the film build method of the first execution mode alternate embodiment, and the timing diagram of RF form is supplied with and applied to expression gas.
Fig. 9 is the profile of the film formation device (vertical CVD device) of expression second execution mode of the present invention.
Figure 10 is in the film build method of second execution mode, and the timing diagram of RF form is supplied with and applied to expression gas.
The figure of Figure 11 A silicon nitride film film forming speed that to be expression obtained by the experiment 3 of second execution mode.
Figure 11 B is the figure of expression by the improvement rate of the experiment 3 silicon nitride film film forming speeds that obtain.
Figure 12 is the roughly block diagram of situation of expression master control part separation structure.
Figure 13 is the timing diagram that the RF form was supplied with and applied to gas in the film build method that is illustrated in the past.
Embodiment
Embodiments of the present invention are described with reference to the accompanying drawings.In the following description, the structural element of said function and structure uses same symbol for having roughly, only carries out repeat specification in the case of necessary.
＜the first execution mode 〉
Fig. 1 is the profile of the film formation device (vertical CVD device) of expression first execution mode of the present invention.Fig. 2 is the cross section plane graph that is illustrated in the part of device shown in Fig. 1.This film formation device 2 contains the unstrpped gas (first handle gas) of the dichlorosilane (DCS) as silane-based gas with supply and contains ammonia (NH as nitriding gas
3) support gas (second handle gas), the mode of being piled into silicon nitride film (SiN) constitutes.
The part that runs through in rotating shaft 20 is provided with, and for example magnetic fluid seal spare 22, supports rotating shaft 20 keeping the bubble-tight while to rotate.Around lid 18 and the lower end of manifold 8, for example be provided with and wait the seal member 24 that forms, the interior sealing of maintenance container by O shape circle.
Rotating shaft 20 is installed in the front end of supporting the joint arm 26 on the elevating mechanism 25 such as support lift for example.Make liftings such as chip support 12 and lid 18 by elevating mechanism 25.In addition, also workbench 16 is arranged on regularly lid 18 1 sides, does not make chip support 12 rotations also can carry out the processing of wafer W.
In the side of manifold 8, connecting the gas supply part branch of the processing region 5 supply predetermined processing gases in container handling 4.The gas supply part branch comprises supports gas supply system (second treating-gas supply system) 28, unstrpped gas feed system (first treating-gas supply system) 30 and purge gas feed system 32.Unstrpped gas feed system 30 is for example supplied with silane-based gas DCS (dichlorosilane) as film forming unstrpped gas.Support gas supply system 28, supply with for example ammonia (NH
3) as optionally carrying out on one side the support gas (second handles gas) that plasmaization reacts with unstrpped gas on one side.Purge gas feed system 32 is supplied with inert gas, for example nitrogen N
2As purge gas.In unstrpped gas and support gas (first and second handle gas), can mix an amount of carrier gas as required, but for the purpose of simplifying the description, not mention below.
Particularly, unstrpped gas feed system 30 has two gas dispersion nozzles 36, and they are made by quartz ampoule, and the sidewall turning that inwardly runs through manifold 8 extends upward (with reference to Fig. 2).On each gas dispersion nozzle 36, along the direction (above-below direction) of its length, the whole wafer W facing on the chip support 12 form a plurality of gas jetting hole 36A with certain interval.Each gas jetting hole 36A forms parallel gas flow with respect to the multi-disc wafer W on chip support 12, in the horizontal direction base feed gas equably roughly.And gas dispersion nozzle 36 is not provided with two, only is provided with one and is fine yet.
Support gas supply system 28 and also have two gas dispersion nozzles 34, they are also made by quartz ampoule, and the sidewall turning that inwardly runs through manifold 8 extends upward.On gas dispersion nozzle 34, along the direction (above-below direction) of its length, the whole wafer W facing on the chip support 12 form a plurality of gas jetting hole 34A with certain interval.Each gas jetting hole 34A forms parallel gas flow with respect to the multi-disc wafer W on chip support 12, roughly supplies with equably in the horizontal direction and supports gas.Purge gas feed system 32 has the gas nozzle 38 of the sidewall setting that runs through manifold 8.
On the sidewall of a part of container handling 4, along the direction configuration gas excitation portion 50 of its height.Opposite side at the container handling 4 relative with gas excitation portion 50 disposes elongated exhaust outlet 52, is used for discharging inner environmental gas and forms vacuum, is to form by for example the sidewall of container handling 4 being cut a part at above-below direction.
Particularly, gas excitation portion 50 has elongated opening 54 up and down, and it forms with the sidewall that certain width cuts container handling 4 along above-below direction.This opening 54 is covered by the quartzy lid of making 56, and this lid combines with the outer wall welding of container handling 4, and has air-tightness.The section of lid 56 is spills, and is outstanding to the outside of container handling 4, and has elongated shape up and down.
Form from the sidewall of container handling 4 by such structure outstanding, and the gas excitation portion 50 of one side direction container handling 4 inner openings.That is, the processing region 5 in the inner space of gas excitation portion 50 and the container handling 4 is communicated with.Opening 54 forms enough length on above-below direction, can cover the whole wafers that remain on the chip support 12 on the short transverse thus.
On the lateral surface of 56 two sidewalls of lid,, dispose a pair of elongated electrode 58 in mode respect to one another along its length direction (above-below direction).To produce the high frequency electric source 60 that plasma uses by supply lines is connected on the electrode 58.By on electrode 58, applying for example high frequency voltage of 13.56MHz, between pair of electrodes 58, form and be used for the high-frequency electric field of activated plasma.In addition, the frequency of high frequency voltage is not limited to 13.56MHz, also can use other frequency, for example 400kHz etc.
In the outside of lid 56, be equipped with by for example quartzy insulation protective jacket 64 that constitutes, cover lid 56.With as the relative part of the electrode 58 of insulation protective jacket 64 inboards, dispose the cooling body (not shown) that constitutes by coolant channel.For example in coolant channel, flow through as the nitrogen that is cooled of cold-producing medium, make electrode 58 coolings.In addition, in the outside of insulation protective jacket 64, be provided with the guard shield (not shown) that covers it and prevent HF leakage.
Near opening 54 outsides of gas excitation portion 50, promptly erect two gas dispersion nozzles 36 of configuration in the both sides in opening 54 outsides (in the container handling 4).The unstrpped gas that contains DCS gas by each the gas nozzle 36A that on gas dispersion nozzle 36, forms towards the center position injection of container handling 4.
In addition, in the exhaust outlet 52 that is provided with gas excitation portion 50 subtends, the exhaust coating member 66 that is " コ " font by the section of quartz manufacturing has been installed, has been covered exhaust outlet by welding.This exhaust coating member 66 extends upward along the sidewall of container handling 4, forms gas vent 68 above container handling 4.Connect the vacuum pumping system GE that vacuum pump etc. is housed at gas vent 68 places.
To surround the mode of container handling 4, be provided with heater 70, be used for ambient gas and wafer W in the heat treated container 4.Near the exhaust outlet 70 in container handling 4, be provided with the thermocouple (not shown) of control heater 70 usefulness.
Have, film formation device 2 comprises the master control part 48 that is made of computer of the action of control device integral body etc. again.Master control part 48, according to the processing parameter that the film forming that pre-deposits at its subsidiary storage area is handled, for example the thickness of the film of Xing Chenging or composition carry out film forming processing as described below.In this storing section stores handle the thickness of the flow of gas and film and relation conduct between the forming control data that prestores.Thereby master control part 48 just can be controlled elevating mechanism 25, gas supply system 28,30,32, gas extraction system GE, gas excitation portion 50 and heater 70 etc. based on the processing parameter or the control data of these storages.
The following describes use and carry out the method (so-called ALD film forming) of film forming at the device shown in Fig. 1.Briefly, in this film build method, base feed gas in the processing region 5 that holds wafer W (film forming is handled gas with first) and support gas (handling gas with second of the first processing gas reaction) form film by CVD on wafer W.
At first, will keep multi-disc at normal temperatures, for example 50～100 chip sizes are that the chip support 12 of the wafer W of 300mm is packed in the container handling 4 that is set in set point of temperature.Vacuumize in container handling 8 then, and maintain under the predetermined process pressure, simultaneously, the temperature of rising wafer is up to being stabilized in the treatment temperature that film forming is used.
Then, by gas dispersion nozzle 36 and 34, when controlling flow respectively, supply with the unstrpped gas that contains DCS gas off and on and contain NH
3The support gas of gas.Particularly, from the gas jetting hole 36A base feed gas of gas dispersion nozzle 36, make to form parallel gas stream with respect to the multi-disc wafer W on the chip support 12.In addition, support gas, make to form parallel gas stream with respect to the multi-disc wafer W on the chip support 12 from the gas jetting hole 36A supply of gas dispersion nozzle 34.Two kinds of gases react on wafer W, form silicon nitride film thus on wafer W.
The support gas of being supplied with by the gas jetting hole 36A of gas dispersion nozzle 34, by the plasma generation area PS between the pair of electrodes 58 time, a part is by plasmaization optionally.At this moment, generate for example N
*, NH
*, NH
2 *, NH
3 *Deng free radical (active seed) (symbol * represents it is free radical).These free radicals flow to the center of container handling 4 from the opening 54 of gas excitation portion 50, supply between the wafer W with the state of laminar flow.
Above-mentioned free radical be adsorbed on the reaction of the lip-deep DCS gas molecule of wafer W, on wafer W, form silicon nitride film thus.And in contrast, on the surface of wafer W, adsorbed the position of free radical, and under the situation that flows through DCS gas, same reaction also can take place, on wafer W, form silicon nitride film.
Fig. 3 is in the film build method of first execution mode, and the timing diagram of RF state is supplied with and applied to expression gas.As shown in FIG. 3, in the film build method of this execution mode, alternatively repeat first to fourth during (first to fourth operation) T1～T4.That is, repeatedly repeat the circulation that is made of T1～T4 during first to fourth, the silicon nitride film that forms in each circulation obtains having the silicon nitride film of final thickness by the lamination of film.
Particularly, between the first phase, among (first operation) T1, (in Fig. 3, be expressed as NH to processing region 5 base feed gases (in Fig. 3, being expressed as DCS) and support gas
3).In the second phase (second operation) T2, stop to processing region 5 base feed gases and support gas.Between the third phase, among (the 3rd operation) T3,, stop to processing region 5 base feed gases when processing region 5 is supplied with support gas.In addition, between the third phase among the T3,, make support gaseous plasmaization in gas excitation portion 50, the support gas of supplying with under the state that is exciting to processing region 5 thus by opening RF power supply 60.Between the fourth phase, among (the 4th operation) T4, stop to processing region 5 base feed gases and support gas.
Second and the fourth phase between T2, T4 use during the cleaning of the residual gas in getting rid of container handling 4.This so-called cleaning, be meant and flowing through N
2In the time of inert gases such as gas, with vacuum exhausts in the container handling 4, or stop the supply of all gas, with vacuum exhausts in the container handling 4, to remove the residual gas in the container handling 4.Moreover, first and the third phase between among T1, the T3, when base feed gas with when supporting gas, can stop the vacuum exhaust in the container handling 4.But, on one side at one side base feed gas with support gas when carrying out vacuum exhaust in the container handling 4, during whole first to fourth, can carry out the vacuum exhaust in the container handling 4 in the All Time of T1～T4 constantly.
In Fig. 3, T1 is set at about 1～20 second between the first phase, and for example about 10 seconds, second phase T2 was set at about 1～20 second, and for example about 10 seconds, T3 was set at about 1～30 second between the third phase, and for example about 10 seconds, T4 was set at about 1～20 second, for example about 10 seconds during the 4th.But these times only simply are examples, are not limited to this numerical value.
As mentioned above, supply contains NH together
3The support gas of gas and contain DCS unstrpped gas during T1 and supply with separately and contain NH
3T3 during the support gas of gas, T2, T4 during intersect to implement cleaning.Can improve its film forming speed significantly in the high-quality while of the silicon nitride film of keeping formation thus.Think following reason is arranged.That is, as T1 between first phase base feed gas together with when supporting gas, the DCS molecule that is adsorbed in wafer surface is by the NH that supplies with simultaneously
3Gas makes part nitrogenize by halves.Therefore, between the first phase among the T1, adsorbance is not having when saturated, and the absorption of DCS gas molecule is being carried out always, and the adsorbance of DCS gas just is higher than the amount in previous methods (flowing through unstrpped gas separately) as a result.T3 between the third phase then is by the NH by plasma exciatiaon
3Gas fully reacts the part that does not have complete reaction to make and form silicon nitride film under the state of high film forming speed.
Above-mentioned film forming is handled and is carried out according to following treatment conditions.The flow of DCS gas for example is 1000sccm (1slm) in the scope of 100～3000sccm.NH
3The flow of gas for example is 1000sccm in the scope of 100～5000sccm.Treatment temperature is lower than common CVD to be handled, and is specially 180～600 ℃ (not containing), for example 550 ℃.When treatment temperature was lower than 180 ℃, can't react did not almost have the accumulation of film.And when treatment temperature is higher than 600 ℃, can form the also poor accumulating film of mass ratio CVD.
Processing pressure is 1Torr among (absorption process) T1 between the first phase for example in the scope of 27Pa (0.2Torr)～1330Pa (10Torr), is 0.3Torr among the T3 that (uses the pecvd nitride operation) between the third phase.During less than 27Pa, film forming speed is lower than realistic scale in processing pressure.Under the situation of processing pressure greater than 1330Pa, abundant activated plasma.
Between the first phase among (absorption process) T1, gas DCS and NH
3Flow-rate ratio [DCS/NH
3] be set in the scope about 1/10～10.As gas NH
3The very few situation of flow-rate ratio under, can not produce and supply with NH simultaneously
3The effect of gas.And work as NH
3Flow-rate ratio when too much, can not produce the body of film forming.
＜experiment 1 〉
1 estimate to use the film build method of first execution mode of timing diagram shown in Figure 3 and the silicon nitride film that forms according to the film build method in the past (ALD method) of timing diagram shown in Figure 13 by experiment.In two embodiment PE1 and PE2 of first execution mode, get NH respectively
3Quantity delivered be 500sccm (0.5slm) and 1000sccm (1slm).In the comparative example CE1 of in the past film build method, get NH
3Quantity delivered be 1000sccm (1slm).The period of film forming is got 160 times altogether.
Fig. 4 is the figure of expression by the thickness data of experiment 1 silicon nitride film that obtains.Fig. 5 is the figure of expression by the experiment 1 silicon nitride film film forming speed that obtains.Fig. 6 is that expression is by the figure of the thickness of testing 1 silicon nitride film that obtains at inner evenness.Fig. 7 is the figure of expression by the experiment 1 silicon nitride film infrared ray diffraction result who obtains." TOP " in Fig. 4～Fig. 7, " CTR " and " BTM " represent to be arranged in the position of semiconductor wafer of top, central authorities and the bottom of chip support respectively.
For at the thickness TH of the silicon nitride film shown in Fig. 4 (nm), in comparative example CE1, with the location independent of wafer, TH is about about 15nm.In two embodiment PE1 and PE2, with the location independent of wafer, TH is about 20nm.That is, can confirm that two embodiment PE1 compare with comparative example CE1 with PE2, silicon nitride film that can the accumulative facies uniform thickness.
For in the film forming speed Rth that is equivalent to each circulation shown in Fig. 5 (nm/ circulation), in comparative example CE1, Rth is about about 0.1nm.In two embodiment PE1 and PE2, Rth is about 0.12～0.13nm.That is, can confirm to compare with comparative example CE1, in two embodiment PE1 and PE2, film forming speed has increased.
For the uniformity PTuni of the thickness shown in Fig. 6 in face (± %), in comparative example CE1, PTuni is about ± 3.5～4.5%, in two embodiment PE1 and PE2, PTuni is about ± 3.0～4.0%.That is, can confirm to compare with comparative example CE1, two embodiment PE1 and PE2 can improve the uniformity of thickness in face.
For the infra-red intensity LD (a.u) that obtains at the infrared ray diffraction shown in Fig. 7, in comparative example CE11,, on LD, demonstrate the peak P1 that expression has " Si-H key " in the position of wave number about 2200 by membranous.CE11 uses with hexachloro-silane (HCD) as handle gas, the silicon nitride film that forms in LP (low pressure)-CVD as a comparative example.On the other hand, in embodiment PE1, LD roughly is smooth on the whole.That is, can confirm to compare embodiment PE1 film forming membranous good with comparative example CE11.
According to the timing diagram of Fig. 3, supply with together and contain NH
3The support gas of gas and contain DCS gas unstrpped gas during T1, do not apply RF, and contain NH supplying with separately
3T3 during the support gas of gas applies RF.The RF state that applies shown in Fig. 8 that can be used in replaces this timing diagram.Fig. 8 is the film build method in the embodiment that first execution mode changes, expression supply gas and the timing diagram that applies RF.
According to the timing diagram of Fig. 8, supply with together and contain NH
3The support gas of gas and contain DCS gas unstrpped gas during T1 and supply with separately and contain NH
3During the support gas of gas during these two of the T3 in, apply RF to excite support gas.In the case, T1 between the first phase excites support gas when flowing through unstrpped gas, absorption DCS and NH on semiconductor wafer W
3Free radical.T3 between the third phase then is by the NH of plasma exciatiaon
3Gas makes the part complete reaction of incomplete reaction, forms silicon nitride film under the state of high film forming speed.
＜experiment 2 〉
Can use N
2Gas replaces NH
3Gas is as nitriding gas.In method, use N according to Fig. 3
2Gas replaces NH
3Gas carries out the film forming experiment 2 of silicon nitride film.Consequently, its film forming speed is the 0.1nm/ circulation.In addition, in the method for Fig. 8, use N
2Gas replaces NH
3Gas carries out the film forming of silicon nitride film, and its film forming speed is the 0.5nm/ circulation.Thereby, can confirm method by Fig. 8, using N
2Gas replaces NH
3Gas can improve film forming speed during as nitriding gas significantly.
＜the second execution mode 〉
Fig. 9 is the profile of the film formation device (vertical CVD device) of expression second embodiment of the invention.The film formation device 2X of second execution mode, except supporting gas supply system (second treating-gas supply system) 28, unstrpped gas feed system (first treating-gas supply system) 30 and purge gas feed system 32, also comprise assist gas feed system (the 3rd treating-gas supply system) 84.84 supplies of assist gas feed system are with unstrpped gas or support all different assist gas of gas.Particularly, assist gas contains the gas that is selected from nitrogen, rare gas, nitrogen oxide gas, in the present embodiment, and by for example N
2Or Ar gas constitutes.For with assist gas feed system 84 relevant portions beyond part, the film formation device 2X shown in Fig. 9 with have identical in fact structure at the film formation device shown in Fig. 12.
Assist gas feed system 84 has common gas dispersion nozzle 34 with support gas supply system 28, therefore just has the gas jetting hole 34A that forms on gas dispersion nozzle 34.For this reason, nozzle 34 connects N through the gas supply pipe road (gas passage) 86 of assist gas feed system 84
2Or the gas source 85 of Ar gas.The flow controller 86B of switch valve 86A and mass flow controller and so on is housed on gas supply pipe road 86.Thus can be at control N
2Or the supply gas Ar gas flow time.As assist gas, can use nitrogen oxide gas to replace inert gases such as nitrogen or rare gas as mentioned above.
As mentioned above, gas dispersion nozzle 34 is made of quartz ampoule, and the sidewall that inwardly runs through manifold 8 bends towards direction and extends.On gas dispersion nozzle 34, form a plurality of gas jetting hole 34A along its length (above-below direction) and across the interval of regulation, make whole wafer W on its subtend chip support 12.Each gas jetting hole 34A forms parallel gas stream facing to the multi-disc wafer W on the chip support 12, supplies with substantially equably in the horizontal direction and supports gas or assist gas.Assist gas feed system 84, can be not yet with support gas supply system 28 common gas dispersing nozzles 34, with gas dispersion nozzle 34 the gas dispersion nozzle that assist gas uses is set simultaneously and gets final product.
The following describes the film build method (so-called ALD film forming) that use is carried out at the device shown in Fig. 9.In general, in this film build method, base feed gas in the processing region 5 that holds wafer W (film forming is handled gas with first) and support gas (handling gas with second of the first processing gas reaction) and aforesaid assist gas (the 3rd handles gas) form film by CVD on wafer W.
At first, will keep multi-disc at normal temperatures, for example 50～100 chip sizes are that the chip support 12 of 300mm wafer W is sent in the container handling 4 that is set in set point of temperature.When vacuumizing and maintaining predetermined process pressure in the container handling 8, the temperature of rising wafer is up to being stabilized in the treatment temperature that film forming is used then.
Then, control flow and supply with the unstrpped gas that contains DCS off and on, contain NH respectively by gas dispersion nozzle 36,34
3Support gas and assist gas.Particularly, from the gas jetting hole 36A of gas dispersion nozzle 36, to form the mode base feed gas of parallel gas stream facing to the multi-disc wafer W on the chip support 12.In addition, from the gas jetting hole 36A of gas dispersion nozzle 34, supply with support gas and assist gas in the mode that forms parallel gas stream facing to the multi-disc wafer W on the chip support 12.DCS gas and NH
3Gas reacts on wafer W, forms silicon nitride film thus on wafer W.
Figure 10 is in the film build method of second execution mode, and the timing diagram of the form of RF is supplied with and applied to expression gas.As shown in Figure 10, in the film build method of this execution mode, (first to fourth operation) T11～T14 during overlapping first to fourth.That is, repeatedly repeat the circulation that constitutes by T11～T14 during first to fourth,, obtain the silicon nitride film of final thickness by being layered in the film of the silicon nitride film that forms in each circulation.
Particularly, between the first phase, among (first operation) T11, (in Figure 10, be expressed as N to processing region 5 base feed gases (in Figure 10, being expressed as DCS) and assist gas on the one hand
2Or Ar), stop to supply with support gas simultaneously and (in Figure 10, be expressed as NH to processing region 5
3).Between the first phase, among the T11, connect RF power supply 60, make the assist gas plasmaization, to the assist gas of processing region 5 supplies under excited state by gas excitation portion 50.In the second phase (second operation) T12, stop to processing region 5 base feed gases simultaneously, support gas and assist gas.Between the third phase, among (the 3rd operation) T13,, stop to processing region 5 base feed gas and assist gass when processing region 5 is supplied with support gas.And between the third phase, among the T13, begin to connect RF power supply 60 from the centre, and will support gaseous plasmaization by gas excitation portion 50, only during inferior, in processing region 5, supply with the support gas under excited state thus among the T13b.Between the fourth phase, among (the 4th operation) T14, stop base feed gas, support gas and assist gas in processing region 5.
Second and the fourth phase between T12, T14, as using during cleaning, to give off the residual gas in container handling 4.This so-called cleaning, be meant and flowing through N
2In the time of inert gases such as gas,, perhaps stop to supply with all gases fully, with vacuum exhaust in the container handling 4, to remove the residual gas in the container handling 4 with vacuum exhaust in the container handling 4.First and the third phase between among T11, the T13, at base feed gas, when supporting gas and assist gas, can stop at the vacuum exhaust in the container handling 4.But,, when carrying out the vacuum exhaust of container handling 4 simultaneously, can during whole first to fourth, continue the vacuum exhaust in the container handling 4 among T11～T14 at base feed gas, support gas and assist gas.
In Figure 10, T11 is set to about 1～20 second between the first phase, for example about 10 seconds, second phase T12 was set to about 1～20 second, for example about 10 seconds, T13 is set to about 1～30 second between the third phase, for example about 20 seconds, inferior during T13b be set to about 1～25 second, for example about 15 seconds, T14 is set to about 1～20 second between the fourth phase, for example about 10 seconds.But these times are only represented an example, are not limited to these numerical value.
As mentioned above, by adding and exciting assist gas, by the active seed promotion decomposition of the unstrpped gas of supply meanwhile of above-mentioned assist gas.The result just can improve the film forming speed of silicon nitride film.At this moment, particularly use N
2Gas not only can promote the decomposition of unstrpped gas during as assist gas, also by the direct chemical combination of active seed of the active seed of nitrogen and silicon and directly form SiN.The result can further improve the film forming speed of silicon nitride film.
In second execution mode, treatment temperature and processing pressure and DCS gas, NH
3The flow of all gases such as gas is all identical with first execution mode.The flow of assist gas is set at the flow that is lower than as unstrpped gas DCS gas, for example gets about about 1/10 of DCS gas flow.
Between the third phase among the T13, through after the stipulated time Δ t, connect RF power supply 60, make support gaseous plasmaization at gas excitation portion 50 places, thus only during inferior T13b supply with the support gas that is in excited state to processing region 5.This so-called preset time Δ t is promptly up to making NH
3The time that gas flow is stable is for example about 5 seconds.But, also can as at first execution mode, during whole supply support gas, all make and support gas in gas excitation portion 50 plasmaizations.So make the stability of flowization of supporting gas just connect the RF power supply later on and produce plasma, can improve the uniformity of the active seed concentration of (short transverse) between the wafer W two sides.
＜experiment 3 〉
Use is carried out evaluation experimental 3 according to forming silicon nitride film at the film build method of second execution mode of timing diagram shown in Figure 10 with according to the film build method in the past (ALD) at timing diagram shown in Figure 13.In two embodiment PE11, PE12 of second execution mode, use N respectively
2Gas and Ar gas are as assist gas.The comparative example CE1 of film build method did not use assist gas in the past, according to carry out (identical in fact with the comparative example CE1 of experiment 1) at the timing diagram shown in Figure 13.The period of film forming 160 times altogether.
Figure 11 A is the film forming speed figure of expression by experiment 3 silicon nitride films that obtain.Figure 11 B is the figure of expression by the experiment 3 silicon nitride film film forming speed improvement rates that obtain.Moreover " TOP " in Figure 11 A, Figure 11 B, " CTR " and " BTM " represent that respectively semiconductor wafer in the chip support is positioned at the position of top, central authorities and bottom.
For the film forming speed Rth (nm/ circulation) that is equivalent in each circulation shown in Figure 11 A, in comparative example CE1, with the location independent of wafer, Rth is about 0.1nm.Using N
2Among the embodiment PE11 of gas as assist gas, Rth is about 0.45～0.55nm.In using the embodiment PE12 of Ar gas as assist gas, Rth is about 0.25～0.4nm.
For at the film forming speed improvement rate IRth (%) shown in Figure 11 B, using N
2Among the embodiment PE11 of gas as assist gas, IRth is about 150～300%.In using the embodiment PE12 of Ar gas as assist gas, IRth is about 300～500%.
That is, CE1 compares with comparative example, confirms that two embodiment PE11, PE12 can increase film forming speed.In addition, the film forming speed of embodiment PE11 also is higher than the film forming speed of embodiment PE12, can think following reason.Promptly as mentioned above, N
2The active seed of gas not only promotes unstrpped gas to decompose, and can directly react the formation silicon nitride with the silicon that is excited.
＜item and the variation instance common〉with first and second execution modes
The method of first and second execution modes is based on as mentioned above that handling procedure implements under the control of master control part 48.Figure 12 is the schematic block diagram of expression master control part 48 structures.Master control part 48 has CPU210, is connecting storage area 212, importation 214 and output 216 etc. therewith.In storage area 212, storing handling procedure and method parameter.Importation 214 comprises the input unit of talking with usefulness with the user, for example keyboard or pointing device, and the driver of storage medium etc.Output 216 outputs are used for the control signal of each equipment of control and treatment device.Figure 12 storage medium 218 that also expression can off line simultaneously.
The method of above-mentioned execution mode can as the program command that is used for moving, be applicable to various semiconductor processing devices by writing with calculating machine-readable getting on the storage medium on processor.Perhaps, this kind program command goes for the various semiconductor processing devices that transmit by communication media.This storage medium is for example disk (floppy disk, hard disk (example is the hard disk in storage compartment 212) etc.), CD (CD, DVD etc.), magneto optical disk (MO etc.), semiconductor memory etc.The computer of control semiconductor processing device action by reading in program stored instruction in the storage medium, moves it and implements said method on processor.
In first and second execution modes, use the silane-based gas of DCS gas as unstrpped gas.But be not limited to this,, can use to be selected from dichlorosilane (DCS), hexachloro-silane (HCD), single silane [SiH as unstrpped gas
4], disilane [Si
2H
6], more than one gas of hexamethyldisilazane (HMDS), tetrachloro silicane (TCS), disilazane (DSA), nitrilotrisilane (TSA) and dual-tert-butyl amino silane (BTBAS).
In addition, in first and second execution modes, can use nitrous oxide [N
2O], the nitrogen oxidizing gas of nitrogen oxide [NO] and so on replaces NH
3Gas, N
2Nitriding gas such as gas are as supporting gas.Can also use oxidizing gas to replace nitriding gas as supporting gas.
In addition, in second execution mode, use rare gas as assist gas, but be not limited to Ar gas, can use He, Ne, Kr, Xe etc.Also can use nitrous oxide [N
2O], nitrogen oxide [NO], nitrogen dioxide [NO
2] wait nitrogen oxide to use as assist gas.
In above-mentioned first and second execution modes,, have and to form the excitation portion 50 of plasma and the combining structure that container handling 4 is made one as film formation device 2.In addition, also excitation portion 50 and container handling 4 can be set respectively, beyond container handling 4, excite NH in advance
3Gas (so-called remote plasma) is supplied with this NH that excites in container handling 4
3Gas.Being not limited to semiconductor wafer as processed substrate, also can be other substrates such as LCD substrate, glass substrate.
For one of skill in the art, additional advantage and improvement all are easily.Therefore, the present invention is not limited to these concrete details and representative embodiments shown here and described at it aspect more widely.Only otherwise depart from the spirit and scope of as defined in the claims inventive concept and equivalent thereof, can carry out variation miscellaneous.
Claims (5)
1. film formation device that semiconductor processes is used is characterized in that: have:
Container handling with the processing region that holds processed substrate,
In described processing region, support the holding components of described processed substrate,
Heat the heater of the described processed substrate in the described processing region,
Discharge the gas extraction system of gas in the described processing region,
Supply with first treating-gas supply system of film forming to described processing region with the first processing gas,
Supply with second treating-gas supply system of handling gas with second of the described first processing gas reaction to described processing region,
Described second of the described processing region supply of subtend handle the excitation mechanism that gas excites selectively,
Control the control section of described device action,
Handle the 3rd treating-gas supply system of the 3rd any all different processing gas of gases to described processing region supply and first and second, the described the 3rd handles gas and described second handles the total supply port of gas, and excited by described excitation mechanism selectively
The described the 3rd handles gas contains the gas that is selected from nitrogen, rare gas, the nitrogen oxide gas,
In order to form film by CVD on described processed substrate, described control section intersects implements following operation:
Supplying with the described first and the 3rd processing gas to described processing region when, stop to supply with first operation of the described second processing gas to described processing region, described first operation has by excitation mechanism, make the described the 3rd handle gas with excited state supply with described processing region during;
Stop to supply with second operation of described first to the 3rd processing gas to described processing region;
Supplying with the described second processing gas to described processing region when, stop to supply with the 3rd operation of the first and the 3rd processing gas to described processing region; With
Stop to supply with the 4th operation of described first to the 3rd processing gas to described processing region.
2. the device described in claim 1, it is characterized in that: described excitation mechanism have with space that described processing region links to each other in, be configured in described second and handle the supply port of gas and the plasma generation area between the described substrate, described second handles gas is excited by described plasma generation area the time.
3. the device described in claim 2 is characterized in that: described plasma generation area has by being attached to electrode and the high frequency electric source in the described container handling, handles the high-frequency electric field that forms between gas supply port and the described substrate described second.
4. the device described in claim 1, it is characterized in that: the structure of described processing region makes that the processed substrate of described multi-disc is set at the described heater heats around the described processing region can hold the processed substrate of multi-disc last having at interval under the stacked state.
5. the device described in claim 1, it is characterized in that: will have more than a plurality of processed substrates at interval and stacked state is contained in described processing region, described first and second handle gas, be supplied to from a plurality of first gas jetting holes and a plurality of second gas jetting hole of arranging facing to the above-below direction of described a plurality of processed substrates respectively, form parallel gas flow with respect to described a plurality of processed substrates.
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| JP2005048059A JP4396547B2 (en) | 2004-06-28 | 2005-02-23 | Film forming method, film forming apparatus, and storage medium |
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| US20070240644A1 (en) | 2006-03-24 | 2007-10-18 | Hiroyuki Matsuura | Vertical plasma processing apparatus for semiconductor process |
| US20070259111A1 (en) * | 2006-05-05 | 2007-11-08 | Singh Kaushal K | Method and apparatus for photo-excitation of chemicals for atomic layer deposition of dielectric film |
| JP6105967B2 (en) * | 2012-03-21 | 2017-03-29 | 株式会社日立国際電気 | Semiconductor device manufacturing method, substrate processing method, substrate processing apparatus, and program |
| DE102015004419A1 (en) * | 2015-04-02 | 2016-10-06 | Centrotherm Photovoltaics Ag | Wafer boat and plasma treatment device for wafers |
| CN112420731B (en) * | 2020-11-17 | 2021-12-17 | 长江存储科技有限责任公司 | Method for forming thin film layer in deep hole and method for manufacturing semiconductor device |
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