CN102345111B - Film forming method and apparatus - Google Patents
Film forming method and apparatus Download PDFInfo
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- CN102345111B CN102345111B CN201110217038.0A CN201110217038A CN102345111B CN 102345111 B CN102345111 B CN 102345111B CN 201110217038 A CN201110217038 A CN 201110217038A CN 102345111 B CN102345111 B CN 102345111B
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Abstract
The invention provides a method which utilizes a film forming apparatus to form a film made of silicon oxide film upon a to-be-processed object. Further provided is a film forming apparatus. The film forming apparatus comprises a processing container, a raw material gas feeding system having a first open-and-close valve capable of feeding raw material gas inside the processing container, a reactive gas feeding system having a second open-and-close valve capable of feeding the reactive gas inside the processing container, and a vacuum venting system having a third open-and-close valve capable of venting the atmosphere gas out the processing container to form vacuum. The adsorption process and the reaction process have multiple alternations amid intervals. The adsorption process comprises the steps of: closing the third open-and-close valve, opening the first open-and-close valve in specified period to feed raw material gas to the processing container, and closing the first open-and-close valve to keep the state regulation period, thus to make the raw material gas be attached to the surface of the to-be-processed object. The reaction process comprises the steps of opening the second open-and-close valve, and feeding reactive gas to the processing container, thus to make the reactive gas and the raw material gas react to form the film.
Description
Technical field
The present invention relates to film and film deposition system that silicon oxide film is piled up on the surface at handled objects such as semiconductor crystal wafers.
Background technology
Generally speaking, in order to manufacture semiconductor integrated circuit, the various process such as film forming process, etch processes, oxide treatment, DIFFUSION TREATMENT, modifying process is carried out to the semiconductor crystal wafer formed by silicon substrate etc. (hereinafter referred to as wafer).Such as film forming process is carried out in the film deposition system of the batch type disclosed in the film deposition system of the one chip disclosed in patent documentation 1, patent documentation 2.As shown in Figure 1, the film deposition system of batch type comprises: the processing vessel 2 of longitudinal type; Be housed in processing vessel 2, make the brilliant boat 4 of the multiple wafer W into handled object for multilayer twelve Earthly Branches; In processing vessel 2, the short transverse along processing vessel 2 extends, and for the dispersing nozzle 8,10 towards brilliant boat 4 base feed gas; Be formed in the venting port 12 of the bottom of processing vessel 2; Vacuum evacuating system 14 that be connected with venting port 12 via pressure-regulating valve 14B, that comprise vacuum pump 16; And around the heating part 6 of processing vessel 2.
And when such as forming silicon oxide film in the film deposition system of Fig. 1, the brilliant boat 4 for supporting multiple wafer W is accommodated in processing vessel 2, wafer W is heated to the temperature such as about 600 DEG C of regulation by heating part 6.Supply the such as silicon unstripped gas as unstripped gas from gas supply part 7 to dispersing nozzle 8, the multiple gas jetting hole 8A arranged from the length direction along dispersing nozzle 8 supply silicon unstripped gas towards wafer W.In addition, supply the such as ozone gas as reactant gases from gas supply part 7 to dispersing nozzle 10, the multiple gas jetting hole 10A arranged from the length direction along dispersing nozzle 10 are towards wafer W ozone supply gas.On the other hand, the inside of processing vessel 2 is exhausted by vacuum evacuating system 14, is maintained at the pressure of regulation.Silicon unstripped gas and ozone gas react, and wafer W piles up silica film.
In addition, sometimes following film is adopted, namely, by replacing open and close valve 8B and the open and close valve 10B of opening and closing gas supply part 7, come alternately repeatedly to supply the unstripped gas containing Si and the ozone gas as oxidizing gas, make to be adsorbed on the unstripped gas containing Si on wafer and ozone gas reacts, form silicon oxide film.It is relatively good that this film has formed film quality, even and if under cryogenic also can the such advantage of film forming.
Patent documentation 1: Japanese Unexamined Patent Publication 09-077593 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-246318 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2006-054432 publication
In addition, in the manufacturing process of semiconducter device, sometimes carry out to construct Wiring structure etc. as wiring containing the stacked operation such as the above-mentioned silicon oxide film of insulating film on the film of metal.When carrying out above-mentioned operation, on the wafers such as silicon substrate, the such as tungsten film etc. as the film containing metal is formed in front operation, this wafer is exposed in the atmospheric pressure atmosphere in dust free chamber (clean room) and carries, or be incorporated in be closed with clean non-active gas atmosphere conveying container in carry.
Now, react as the oxygen in the clean atmosphere gas in the surface of the tungsten film of the above-mentioned film containing metal and dust free chamber, moisture, or react with oxygen, moisture that trace in conveying container exists, thus can be surperficial with very thin thickness self-assembling formation metal oxide film at this tungsten film.
Because the metal oxide film of this self-assembling formation becomes the reason making the electrical specification of semiconducter device be deteriorated, so or suppress the increase of the thickness of this metal oxide film or remove this metal oxide film, though it is good to remove this metal oxide film, but it is not correspondingly can increase process number with the operation carrying out removing this metal oxide film, so preferred.Therefore, in the past, generally, do not remove metal oxide film and directly on this metal oxide film, form silicon oxide film by CVD as described above.
On the other hand, when merely applying the stacked silicon oxide film of CVD in the past, due to the oxidizing gas of the film forming gas as a side, the phenomenon that the thickness producing metal oxide film on the contrary increases, its result, can produce and make the electrical specification of semiconducter device reduce such problem (such as patent documentation 3) significantly.When particularly this metal oxide film is thickening, not only makes electrical specification reduce further as described above, also exist and produce the such problem of shape defect because of formed needle crystal.
Summary of the invention
The present invention accordingly provides a kind of film and the film deposition system that can be suppressed this thickness by the thickness of control metal oxide film, and this metal oxide film is present in the interface between the film containing metal of the substrate of film and this film be made up of silicon oxide film.
The formation of the present inventor to silicon oxide film is concentrated on studies, its result, find that the increase of the thickness of metal oxide film is relevant with the diffusion of the ozone as reactant gases, and obtain following opinion, thus completing the present invention, this opinion is, by being enclosed in processing vessel by unstripped gas in the absorption process of absorption unstripped gas, a large amount of unstripped gas can be made to be adsorbed on crystal column surface, the impact that ozone brings can be suppressed thus.
According to the 1st technical scheme of the present invention, a kind of film using film deposition system to form the film be made up of silicon oxide film on handled object is provided, the surface of this handled object is formed with the film containing metal, this film deposition system comprises: unstripped gas plenum system, it has the 1st open and close valve, can to base feed gas in above-mentioned processing vessel; Reactant gases plenum system, it has the 2nd open and close valve, can to supply response gas in above-mentioned processing vessel; Vacuum evacuating system, it has the 3rd open and close valve, the atmosphere in above-mentioned processing vessel can be lined up vacuum.In this film, off period ground alternate repetition repeatedly this absorption process and reaction process is there is between absorption process and reaction process, this absorption process is, close above-mentioned 3rd open and close valve of above-mentioned vacuum evacuating system, open above-mentioned 1st open and close valve the 1st specified time limit of above-mentioned raw materials gas supply system, after above-mentioned processing vessel supply above-mentioned raw materials gas, close the 1st open and close valve, under the state keeping above-mentioned 1st open and close valve to close for the 2nd specified time limit, make above-mentioned raw materials gas adsorption in above-mentioned processing vessel in the surface of above-mentioned handled object; This reaction process is, opens above-mentioned 2nd open and close valve of above-mentioned reactant gases plenum system, in above-mentioned processing vessel, supplies above-mentioned reactant gases, make above-mentioned reactant gases and above-mentioned raw materials gas react and form film.
According to the 2nd technical scheme of the present invention, provide a kind of film deposition system, it comprises: processing vessel, and it can accommodate handled object; Maintaining part, it is for keeping above-mentioned handled object; Heating part, it is for heating above-mentioned handled object; Unstripped gas plenum system, it has open and close valve, can to base feed gas in above-mentioned processing vessel; Reactant gases plenum system, it has open and close valve, can to supply response gas in above-mentioned processing vessel; Vacuum evacuating system, it has open and close valve, the atmosphere in above-mentioned processing vessel can be lined up vacuum; Apparatus control portion, its control device entirety makes this device entirety perform the film of the 1st technical scheme.
Accompanying drawing explanation
Enroll in this specification sheets the accompanying drawing forming its part and represent embodiments of the present invention, together play with the detailed description of above-mentioned embodiment bright and following in general the effect that principle of the present invention is described.
Fig. 1 is the synoptic chart of the film deposition system of the batch type representing corresponding technology.
Fig. 2 is the pie graph of the film deposition system representing embodiments of the present invention.
Fig. 3 is the graphic representation of the action of each valve when representing the film carrying out embodiments of the present invention.
Fig. 4 is the amplification view in the cross section representing the multilayer film formed with the film of embodiments of the present invention.
During Fig. 5 is the maintenance representing unstripped gas and the graphic representation of the relation of the rate of film build of every 1 circulation.
Fig. 6 is the graphic representation of the relation of the thickness representing every rate of film build of 1 circulation and the metal oxide film of tungsten.
Fig. 7 contains the figure of the oxidized reason of near interface between the film of metal and silicon oxide film for illustration of the film containing metal at this.
Fig. 8 is the graphic representation of the relation of the thickness representing every rate of film build of 1 circulation and the metal oxide film of titanium nitride film.
Embodiment
Film according to the embodiment of the present invention and film deposition system, can suppress this thickness by controlling the thickness of metal oxide film, this metal oxide film is present in the interface between the film containing metal of the substrate of film and this film be made up of silicon oxide film.Its result, can prevent the reduction of electrical specification, and can also prevent the generation of shape defect by suppressing the thickness of above-mentioned metal oxide film.
Below, film and the film deposition system of embodiments of the present invention are described in detail in detail based on accompanying drawing.Fig. 2 is the pie graph of an example of the film deposition system representing embodiments of the present invention, and Fig. 3 is the graphic representation of the action of each open and close valve when representing the film carrying out embodiments of the present invention.
Here, be described for following situation, that is: as unstripped gas, be used as 3DMAS (Tris (dimethylamino) silane:SiH (N (CH of the organic raw material containing Si
3)
2)
3), be used as the ozone of oxidizing gas as reactant gases, form the silicon oxide (SiO as film
2) film.
As shown in Figure 2, this film deposition system 20 has and can accommodate multiple processing vessels 22 as the semiconductor crystal wafer W of handled object.This processing vessel 22 has the dual pipe structure be made up of the inner core 24 of lengthwise and the urceolus 26 of lengthwise, and this inner core 24 is in the cylindrical shape having top; This urceolus 26 is in the cylindrical shape having top.Urceolus 26 to be separated with the mode at the interval of regulation around inner core 24 between the periphery of inner core 24 and the inner circumferential of urceolus 26.
Above-mentioned inner core 24 and urceolus 26 are formed by quartz, underpart opening.Such as when collecting diameter is the wafer W of 300mm, the diameter of processing vessel 22 is about 400 ~ 500mm.The internal capacity of processing vessel 22 depends on the collecting number of wafer W, is about 200 liters when such as accommodating the wafer W of maximum about 150.
In the bottom of urceolus 26, be connected with the manifold (manifold) 28 of the such as stainless steel with cylindrical shape by containment members 30 such as O RunddichtringOs airtightly, utilize this manifold 28 to support the bottom of urceolus 26.In addition, this manifold 28 is supported by not shown pedestal (Baseplate).And to be provided with at the inwall of manifold 28 there is annular supporting station 32, utilize this supporting station 32 to support the bottom of inner core 24.
The brilliant boat 34 as wafer maintaining part is contained in the inner core 24 of processing vessel 22.The multiple wafer W as handled object are kept using the spacing of regulation in brilliant boat 34.In the present embodiment, utilize brilliant boat 34 roughly equidistantly to keep that diameter is 300mm to multilayer, the wafer W of such as about 50 ~ 100.Brilliant boat 34 can be elevated as described later, through the lower openings of manifold 28, accommodates in inner core 24, takes out from inner core 24 from the below of processing vessel 22.Brilliant boat 34 is such as made by quartz.
In addition, when brilliant boat 34 is by collecting, the lower openings as the manifold 28 of the lower end of processing vessel 22 is closed by the cap 36 be such as made up of quartz, stainless steel plate.In order to maintain stopping property, between the bottom of processing vessel 22 and cap 36, be folded with the containment members 38 such as such as O RunddichtringO.Brilliant boat 34 is positioned in mounting table 42 across the heat-preservation cylinder 40 of quartz, and this mounting table 42 is supported by the upper end of turning axle 44, and this turning axle 44 runs through the cap 36 for the lower ending opening of opening and closing manifold 28.
Between the hole run through for turning axle 44 and turning axle 44 of cap 36, be such as provided with magnetic fluid seal 46, turning axle 44 is hermetically sealed and can be supported rotatably thus.Turning axle 44 is installed in the front end of the arm 50 on hoisting appliances 48 such as being supported in such as boat elevator, and brilliant boat 34 and cap 36 etc. can be made to be elevated integratedly.In addition, also mounting table 42 can be fixedly arranged at cap 36 side, not make brilliant boat 34 carry out film forming process to wafer W rotatably.
The heating part 52 that the well heater such as made by carbon filament (carbon wire) around processing vessel 22 forms is provided with at the sidepiece of processing vessel 22, thus, the processing vessel 22 be arranged in inside this heating part 52 is heated with the wafer W of this processing vessel 22.And, in manifold 28, be provided with the unstripped gas plenum system 54 for base feed gas, the reactant gases plenum system 56 for supply response gas and the sweeping gas plenum system 58 for supplying the non-active gas as sweeping gas.
Specifically, unstripped gas plenum system 54 has gas jet 60, and this gas jet 60 is made up of quartz, has L-shaped shape, installs in the mode of the inner side extending through manifold 28 airtightly.The whole region of this gas jet 60 along short transverse in inner core 24 extends, and is formed with multiple gas jetting hole 60A with the spacing specified, can from laterally to each wafer W base feed gas be bearing in brilliant boat 34.Gas jet 60 is connected with gas passage 62.
The open and close valve 62B of the flow director 62A as mass flow controller and the start and stop (blocking) for gas circulation is provided with successively in gas passage 62, therefore, the flow that can control gas jet 60 as required makes unstripped gas circulate, stops.Here, as unstripped gas, as described above with the 3DMAS containing Si.3DMAS as this liquid starting material is vaporized device 63 and gasifies, and is carried by vector gas.Specifically, by adjusting the temperature of 3DMAS with gasifier 63, the vapour pressure of control 3DMAS, control the amount of the 3DMAS that will gasify.As carrier gas physical efficiency N
2the non-active gas of the rare gas such as gas and Ar, He etc.In addition, also can carry without vector gas the 3DMAS gas be vaporized.
In the present embodiment, the gasifier of baking (baking) mode is used as gasifier 63.This gasifier has the material container 63T for storing 3DMAS and the well heater 63A for heating raw container 63T, by the 3DMAS in heating raw container, 3DMAS is gasified, directly to importing gasification 3DMAS gas in processing vessel 22.In this case, without vector gas.In gasifier 63, be also provided with pressure warning unit 63B, the temperature of control 3DMAS makes the vapour pressure of 3DMAS higher than the pressure in processing vessel 22.This control utilizes not shown temperature regulator to carry out.
In addition, as gasifier 63, the gasifier of injection (injection) mode can also be used.In this gasifier, supply when gasifying 3DMAS gas to make stability of flow in processing vessel 22, need in processing vessel 22, not discharge unstripped gas with passing into unstripped gas in about 5 ~ 10 seconds, so have to waste organo metallic material gas at high price.Thus, the viewpoint effectively utilized from raw material preferably uses the gasifier of roasting mode.
In addition, reactant gases plenum system 56 has gas jet 64, and this gas jet 64 is made up of quartz, has L-shaped shape, installs in the mode of the inner side extending through manifold 28 airtightly.The whole region of this gas jet 64 along short transverse in inner core 24 extends, and is formed with multiple gas jetting hole 64A with the spacing specified, can from laterally to each wafer W supply response gas be bearing in brilliant boat 34.Gas jet 64 is connected with gas passage 66.The open and close valve 66B of the flow director 66A as mass flow controller and the start and stop (blocking) for gas circulation is provided with successively in gas passage 66, therefore, the flow that can control gas jet 64 as required makes reactant gases circulate, stops.Here, as reactant gases, use ozone (O as described above
3).
And sweeping gas plenum system 58 has gas jet 68, this gas jet 68 is made up of quartz, has L-shaped shape, installs in the mode of the inner side extending through manifold 28 airtightly.The whole region of this gas jet 68 along short transverse in inner core 24 extends, and is formed with multiple gas jetting hole 68A with the spacing specified, can from laterally supplying sweeping gas to each wafer W be bearing in brilliant boat 34.Gas jet 68 is connected with gas passage 70.The open and close valve 70B of the flow director 70A as mass flow controller and the start and stop (blocking) for gas circulation is provided with successively in gas passage 70, therefore, the flow that can control gas jet 68 as required makes sweeping gas circulate, stops.In the present embodiment, as sweeping gas, use nitrogen as described above.In other embodiment, as sweeping gas, also nitrogen can be substituted with rare gas such as Ar, He.
And, the each side of gas jet 60,64,68 concentrated setting in inner core 24 is (in illustrative example, due to the relation in space, gas jet 68 is represented with other gas jet 60,64 contrary sides), inner core 24 with this each gas jet 60,64, on 68 relative sidewalls, be formed with the larger multiple gas communication hole 72 of diameter along above-below direction arrangement.Therefore, supplied from gas jet 60,64,68 gas that comes between wafer through flowing in the horizontal direction, be directed to the gap 74 between inner core 24 and urceolus 26 through gas communication hole 72.
And, in the upper side of manifold 28, be formed with the venting port 76 be connected with the gap 74 between inner core 24 and urceolus 26, be provided with the vacuum evacuating system 78 for carrying out vacuum exhaust to processing vessel 22 at this venting port 76 place.Specifically, vacuum evacuating system 78 has the exhaust channel 80 be connected with venting port 76, open and close valve 80B and vacuum pump 82 is provided with successively in the midway of exhaust channel 80, can while carry out pressure adjusting while carry out vacuum exhaust to the atmosphere in processing vessel 22, the aperture of the spool of this open and close valve 80B can adjust, by changing the pressure in the aperture adjustment processing vessel 22 of this spool.The spool being located at the open and close valve 80B of exhaust channel 80 at random can adjust in the scope from fully open position to full close position.And when spool is full cut-off, the gas from processing vessel 22 is opened and closed valve 80B and fully blocks.
In addition, in order to be controlled to the action of film device 20 entirety, there is the apparatus control portion 84 be such as made up of computer.Utilize apparatus control portion 84, control the start and stop of the supply of each gas, comprise vacuum evacuating system 78 open and close valve 80B spool aperture adjustment on-off action, operation pressure, film-forming temperature etc., in film deposition system 20, implement film forming process.Such control is carried out by the computer program utilizing apparatus control portion 84 to perform for being controlled to film device 20 molar behavior.Such computer program is stored in storage media 86, is loaded (load) in apparatus control portion 84.As storage media 86, floppy disk, CD (Compact Disc), hard disk, flash memory or DVD etc. can be used.
Then, with reference to Fig. 4 ~ Fig. 7, film that carry out with the film deposition system 20 formed as above, embodiments of the present invention is described.Fig. 4 is the amplification view in the cross section representing the multilayer film formed with this film, Fig. 5 is the graphic representation of the relation representing maintenance (hold) period of unstripped gas and the rate of film build of every 1 circulation, Fig. 6 is the graphic representation of the relation representing every rate of film build of 1 circulation and the thickness of metal oxide film, and Fig. 7 is the figure for illustration of the oxidized reason of the near interface of the film containing metal between the film containing metal and silicon oxide film.As described above, the action below illustrated is carried out based on the program be stored in storage media 86.
And in the following description, wafer W can be such as Silicon Wafer, in its surface, in front operation, form the such as tungsten film as the film containing metal.This wafer W is housed in conveying container, and the film deposition system in the past in operation is transported to film deposition system 20.Now, the atmosphere of conveying container inside is maintained at the air atmosphere identical with the atmosphere in dust free chamber or clean non-active gas atmosphere.And, under the oxygen in the air atmosphere that tungsten film surface is exposed in dust free chamber, moisture, or be exposed under trace is present in oxygen in clean non-active gas atmosphere, moisture.Its result, is formed with native metal oxide film on tungsten film surface with very thin thickness.
Brilliant boat 34 is taken out by the lower openings from manifold 28, and is maintained at the below of processing vessel 22.Thus, brilliant boat 34 is such as maintained at normal temperature, and now, multiple (such as 50) wafer W are accommodated in brilliant boat 34.Then, the brilliant boat 34 containing wafer W rises, and is loaded in processing vessel 22.The bottom (lower openings of manifold 28) of processing vessel 22 is closed by cap 36, and processing vessel 22 is closed.
In addition, now, the temperature in processing vessel 22 is maintained at lower than film-forming temperature and higher than normal temperature temperature.
Then, the vacuum pump 82 of vacuum evacuating system 78 starts, and lines up vacuum by processing vessel 22, and utilizes open and close valve 80B, makes the pressure in processing vessel 22 maintain the operation pressure of regulation.In film process, vacuum pump 82 and open and close valve 80B are continuously driven.
In addition, supplying electric power by increasing to heating part 52, wafer W being heated to film-forming temperature and being stable at this temperature, afterwards, as shown in the following, flow control being carried out while carry out film forming process to the process gas of the regulation of carrying out needed for film forming process.
That is, supply as the 3DMAS gas containing Si gas, from gas jet 64 ozone supply of reactant gases plenum system 56 from the gas jet 60 of unstripped gas plenum system 54.And supply the N as sweeping gas from the gas jet 68 of sweeping gas plenum system 58
2gas.
The each gas supplied is bearing on brilliant boat 34 between wafer to flow in multilayer in the horizontal direction, the gap 74 flowed between inner core 24 and urceolus 26 through the gas communication hole 72 in opposition side.Afterwards, these gases are discharged by the venting port 76 of vacuum evacuating system 78 from the lower end being located at urceolus 26.
Then, reference Fig. 3 is while specifically describe the situation of the supply of each gas.As described above, here unstripped gas and reactant gases are alternately supplied repeatedly.(A) of Fig. 3 represents the on-off action of the open and close valve 62B of unstripped gas, (B) of Fig. 3 represents the on-off action of the open and close valve 66B of reactant gases, and (C) of Fig. 3 represents the on-off action (aperture of spool) of the open and close valve 80B of vacuum evacuating system.
Namely, alternately repeatedly carry out repeatedly following each operation successively, form film, this each operation comprises: absorption process, as shown in (A) of Fig. 3, during the open and close valve 62B opening unstripped gas specifies, temporarily the unstripped gas of supply containing Si, makes unstripped gas be adsorbed in wafer W surface; Deairing step, stops the supply of unstripped gas, is exhausted the atmosphere gas in processing vessel 22; Reaction process, as shown in (B) of Fig. 3, opens the ozone of open and close valve 66B supply as reactant gases of reactant gases, ozone is reacted with absorption unstripped gas on the wafer surface, forms the SiO that thickness is thinner
2film; Deairing step, the supply of stopped reaction gas, is exhausted the atmosphere gas in processing vessel 22.
At this, be 1 circulation during from 1 absorption process to next absorption process, in 1 circulation, form very thin (1 molecular layer or several molecular layer degree) film as described above.The time T1 of absorption process in 1 circulation and the time T2 of reaction process is about 60sec, and the time T3 of deairing step and the time T4 of later half deairing step of the first half in 1 circulation are about 10sec respectively.In addition, in each deairing step, also can supply N2 sweeping gas simultaneously.Its result, forms film as shown in Figure 4.That is, before film forming process, as shown in (A) of Fig. 4, be formed with the film 100 containing metal be such as made up of tungsten film in wafer W surface, on film 100 surface that this contains metal, in wafer conveying, form native metal oxide film 102 as described above.In the present embodiment, because the film 100 containing metal is tungsten films, therefore metal oxide film 102 is such as WOx (x: positive integer).After film forming process, as shown in (B) of Fig. 4, metal oxide film 102 forms the film 104 be made up of silicon oxide film.Now, unstripped gas remained on hermetically as described later in processing vessel 22, energy reducing metal oxide film 102, controls the thickness of metal oxide film 102.
Here, in the film of present embodiment, not all base feed gas in the whole process of absorption process, but as shown in (A) of Fig. 3, only in absorption process initial 1st specified time limit t1 open open and close valve 62B, unstripped gas is circulated, afterwards, close open and close valve 62B, placement the 2nd h specified time limit.And, as shown in (C) of Fig. 3, in the whole process of absorption process T1, all close the open and close valve 80B of vacuum evacuating system.Unstripped gas is only in initial t1 circulation the 1st specified time limit, aftertreatment the 2nd specified time limit h, the open and close valve 62B of unstripped gas and the open and close valve 80B of vacuum evacuating system is all closed, so unstripped gas is closed (delay) in processing vessel 22.Its result, has a large amount of unstripped gas in wafer W surface and metal oxide film 102 surface adsorption.Now, as described later, by adjusting the length of the 2nd specified time limit (hereinafter also referred to " during maintenance ") h, the thickness of above-mentioned metal oxide film 102 can be controlled.
The flow of the unstripped gas in initial 1st specified time limit t1 is about 10 ~ 500sccm.In addition, the pressure in the processing vessel 22 of absorption process T1 is after initial sharply rising, and while closing the open and close valve 62B of unstripped gas, become constant, pressure now also depends on the feed rate with unstripped gas, such as, be about 667Pa.
Then, after absorption process terminates, the deairing step T3 of first half is entered.That is, under the state that stopped all gas supply, the open and close valve 80B of vacuum evacuating system is placed in standard-sized sheet, utilizes vacuum pump 82 promptly to discharge the gas remained in processing vessel 22.In addition, in this case, also can be used for the discharge promoting entrap bubble to the N2 gas as sweeping gas.Thus, the concentration of the unstripped gas (3DMAS) in processing vessel 22 sharply reduces.
Then, reaction process T2 is entered.Here, as shown in (B) of Fig. 3, open the open and close valve 66B of reactant gases, within the whole period of reaction process T2, supply the ozone as reactant gases.The open and close valve 80B of vacuum evacuating system now can standard-sized sheet, as long as the free air delivery of gas is enough, spool also can be the aperture of less than 100%, and in illustrative example, the constant opening degree of such as spool is 50%.
In addition, now, the O of 6.5 per minute standard liters (slm) is such as supplied to ozonizer
2produce 200g/Nm
3the ozone of left and right, supply is containing the reactant gases of the ozone of this amount.By the supply of ozone, react with the unstripped gas being adsorbed on wafer W surface, formed and form film 104 by silicon oxide.In this case, in film in the past, ozone is being adsorbed on diffusion in the unstripped gas of crystal column surface, film 104, and is oxidized the surface of the film 100 containing metal of lower floor, causes the thickness of metal oxide film 102 to increase.
But, in the present embodiment, set the maintenance period h of unstripped gas as described above, unstripped gas is made suitably to be adsorbed in crystal column surface, so the diffusion of ozone is suppressed, the increase of metal oxide film 102 can be suppressed, moreover, can also utilize the length of maintenance period h that the thickness of metal oxide film 102 is reduced on the contrary.
Like this, after reaction process T2 terminates, enter later half deairing step T4.That is, stop the supply of all gas and the open and close valve 80B of vacuum evacuating system is set to standard-sized sheet, utilizing vacuum pump 82 promptly to discharge the gas remained in processing vessel 22.In addition, in this case, also can be used for the N as sweeping gas
2gas and promote the discharge of entrap bubble.Thus, the film formation process of 1 circulation terminates, and repeated multiple times each operation of carrying out 1 circulation, can obtain the film with required thickness, the film 104 be namely made up of silicon oxide as required.In addition, in film forming process, operation pressure is maintained at from basis pressure (base pressure) (such as about 13.3Pa) in the scope of 133.3Pa.
As described above, according to the present embodiment, in the absorption process T1 of base feed gas, setting is by the open and close valve 62B of unstripped gas and the open and close valve 80B of vacuum evacuating system 78 together closes, unstripped gas is enclosed in the maintenance period h externally do not flowed out in processing vessel 22, unstripped gas is made suitably to be adsorbed in wafer W surface, so the thickness of the metal oxide film 102 be formed naturally can be suppressed.Particularly by the length of this maintenance of adjustment period h, energy reducing metal oxide film 102, controls the thickness of this metal oxide film 102.Its result, can suppress the thickness of metal oxide film 102, prevents the reduction of electrical specification, and can also prevent shape defect.
evaluation experimental and result thereof
Then, illustrate above-mentioned explanation, utilize embodiments of the present invention to the result of the evaluation experimental that film carries out.Fig. 5 be represent maintenance during and the graphic representation of relation of rate of film build of every 1 circulation, Fig. 6 is the graphic representation of relation of thickness representing the rate of film build of every 1 circulation, the film surface containing metal and metal oxide film.Here, the time T2 of reaction process is fixed between 1 ~ 30sec, the open and close valve 62B of unstripped gas open the 1st specified time limit t1 be fixed between 1 ~ 30sec.And, by making the time T1 of absorption process change, make namely to keep period h (=T1-t1) to change in the open and close valve 62B pent time of absorption process Raw gas.
In Figure 5, as transverse axis during keeping, using the rate of film build of every 1 circulation as the longitudinal axis.And as unstripped gas, circulation contains the 3DMAS as the raw material of Si, the ozone that circulates as reactant gases (oxygen containing 10Vol% ozone).In addition, as film 100 tungsten film containing metal, with the Silicon Wafer of the metal oxide film 102 with the tungsten be formed naturally on this tungsten film surface.Here, the total supply of 3DMAS is set as 1/4 of comparative example (in the past condition).Wafer temperature during film forming is 550 DEG C, and operation pressure (maximum value) is 1.2kPa.And as comparative example, during not setting maintenance, ground alternately base feed gas and reactant gases, form silicon oxide film.Processing condition beyond the action of each open and close valve are the condition identical with the situation of the film of above-mentioned present embodiment.That is, in this comparative example, 4 times of time of absorption process, to be the total supply of 30sec, 3DMAS be the as described above total supply of the film of present embodiment.
From Fig. 5 clearly, as in the present embodiment, make in the scope of maintenance period h about from 10sec to 115sec longer, the rate of film build of every 1 circulation in the scope being recycled to 0.21nm/ circulation left and right from 0.1nm/ more in roughly becoming large to rectilinearity.This reason is, period h is longer in maintenance, and the unstripped gas being adsorbed on wafer W surface more increases, and its result, rate of film build is also higher.
In addition, as secondary effect, known under the condition in the past of supply X gram of 3DMAS, rate of film build is 0.13nm/ circulation left and right, but, when the condition of present embodiment, although the amount of the raw material supplied reduces to 1/4, but during extending maintenance, rate of film build is in rising roughly point-blank.And, during maintenance be roughly 40sec time, rate of film build is roughly the same with the situation of condition in the past.That is, known here, if be set as more than 40sec by during maintenance, although then the total supply of raw material reduces to 1/4, the rate of film build roughly equal or higher with the situation of condition in the past still can be obtained.In other words, the known operation by carrying out each open and close valve as in the present embodiment, cuts down the total supply of raw material significantly while can maintaining the rate of film build equal with condition in the past.
Then, the metal oxide film (W0 of the tungsten corresponding with rate of film build is measured
x) thickness.Its result is shown in Fig. 6.The thickness of metal oxide film is measured by XPS (x-ray photoelectron power spectrum).This metal oxide film be present in as described above by tungsten form containing metal film 100 and by silicon oxide (SiO
2) metal oxide film (WO at interface between the film 104 that forms
x) 102.
The thickness initial value of the tungsten metal oxide film 102 be formed naturally before carrying out film forming process is 1.1nm.In addition, the representational value of maintenance period h is described in figure 6.Curve A in Fig. 6 represents the characteristic of unstripped gas 3DMAS when film-forming temperature is 550 DEG C of film forming.From Fig. 6 clearly, when rate of film build is little, the thickness of metal oxide film 102 becomes larger than initial value, and, along with rate of film build becomes large, the thickness of metal oxide film 102 sharply reduces, and rate of film build is that the thickness of about 0.115nm/ circulation time metal oxide film 102 becomes the value roughly the same with initial value.And when rate of film build increases further, the thickness reduction degree of metal oxide film 102 slows down thereupon.
Like this, the known maintenance period h by adjusting unstripped gas makes rate of film build change, and can control to be present in the film 100 containing metal and film (SiO
2) metal oxide film (the such as W0 at interface between 104
x) 102 thickness.Known particularly by rate of film build is set greater than equal 0.115nm/ circulation, the thickness of metal oxide film 102 can be suppressed and make the thickness of this metal oxide film 102 be reduced to below this initial value.In other words, known in order to make the thickness of metal oxide film 102 for below this initial film thickness, here, as long as will the length of period h be kept to be set as more than 23sec (rate of film build: be more than or equal to 0.115nm/ circulation).
Here, when the rate of film build of every 1 circulation is less than 0.115nm/ circulation, the thickness of metal oxide film becomes the reason thicker than initial value as described below.Namely, as shown in (A) of Fig. 7, when the quantity of molecule 1 10 of unstripped gas of silicon on the surface being adsorbed in the metal oxide film 102 be formed naturally on film 100 surface containing metal is few, gap between molecule 1 10 is large, and the ozone 112 imported afterwards easily spreads through gap as shown in arrow mark.Its result, the ozone easily spread in gap arrives metal oxide film 102 and the film 100 containing metal, further oxidized metal oxide film 102 and the film 100 containing metal, and the thickness of metal oxide film 102 itself is thickening.
As shown in (B) of Fig. 7, when the rate of film build of every 1 circulation increases, the quantity being adsorbed on the molecule 1 10 of the unstripped gas of the silicon on metal oxide film 102 becomes many, the gap smaller between molecule 1 10.Its result, ozone 112 is difficult to through gap, thus suppresses the oxidation of the film 100 containing metal.
In addition, rate of film build is more than or equal to 0.115nm/ circulation time, and the little reason of the Film Thickness Ratio initial value of metal oxide film 102 as described below.That is, because produce reductive action, so the metal oxide film 102 be formed naturally is reduced under reductive action under the film-forming temperature of about 550 DEG C here of the unstripped gas containing silicon itself.Its result, the thickness of the initial value of this metal oxide film 102 as shown in (A) of Fig. 4 is after the film forming of film 104, and as shown in (B) of Fig. 4, metal oxide film 102 is thinning.
According to the above results, when unstripped gas is 3DMAS, the film-forming temperature in preferred each operation is more than 550 DEG C, particularly in order to make the thickness of metal oxide film 102 be below initial value, preferably maintenance period h is set as at least more than 23sec.But the higher limit of this temperature is about 600 DEG C, from the viewpoint of ALD (or MLD) not preferable temperature higher than about 600 DEG C.
In addition, as the experiment added, experiment when to have carried out with 3DMAS be 450 DEG C as unstripped gas, film-forming temperature using condition similar to the above.Period h is now kept only to adopt this kind of setting of 23sec.Its result, as shown in the some B in Fig. 6, rate of film build is 0.088nm/ circulation, and the thickness of the metal oxide film of tungsten is 1.77nm, thicker than initial value 1.1nm.Its result shows, and compared with 450 DEG C, film-forming temperature is preferably 550 DEG C.
In addition, unstripped gas is changed to DIPAS (diisopropylaminoethyl silane) as the identical organic source of amino silicone methane series from 3DMAS, tests under condition same as described above.Its result is represented by some C, the D in Fig. 6.The processing condition of some C are that maintenance period h is 23sec, and film-forming temperature is 450 DEG C.And the processing condition of some D are that maintenance period h is 23sec, and film-forming temperature is 300 DEG C.
As shown in Figure 6, the rate of film build of some C is 0.15nm/ circulation, and the thickness of tungsten metal oxide film is identical with initial value, is 1.1nm.And the rate of film build of some D is 0.185nm/ circulation, and the thickness of tungsten metal oxide film is identical with initial value, is 1.1nm.
Like this, as shown in some C, D, when using DIPAS replacement 3DMAS to be used as raw material, even if film-forming temperature is the lower temperature in the scope of less than 450 DEG C, such as 300 ~ 450 DEG C, rate of film build is also larger, and the adsorptive capacity of silicon is many, so the growth of tungsten metal oxide film can be suppressed.
In above each experiment, employ tungsten film as the film 100 containing metal, the situation employing the film 100 that the alternative tungsten film of titanium nitride film (TiN) is used as containing metal is also tested.Fig. 8 is the graph of relation of the thickness representing every rate of film build of 1 circulation and the metal oxide film of titanium nitride film.The initial film thickness of this metal oxide film is 2.7nm.In the same manner as the situation shown in above-mentioned Fig. 6, maintenance period h is changed from 5sec to 113sec.
As shown in Figure 8, here, during prolongation maintenance, along with the increase of rate of film build, the linearly reduction of thickness of titanium metal oxide film.And when rate of film build is little, the thickness of metal oxide film becomes also thicker than initial value, and the thickness that rate of film build is about the metal oxide film of 0.11nm/ circulation time is roughly the same with initial film thickness.And when rate of film build increases further, the thickness of metal oxide film increases further along with rate of film build and reduces further.Here, the thickness of metal oxide film can be made to be reduced to 1.7nm.
In addition, in above embodiment, be illustrated for the situation employing tungsten film and titanium nitride film as the film containing metal, but, the film that should contain metal comprises the film of the nitride of metallic membrane and metal, specifically, as the above-mentioned film containing metal, can use from a kind of film selected in the group be made up of tungsten film, tungsten nitride film, titanium film, titanium nitride film, tantalum film, nitrogenize tantalum film.
And, in the above-described embodiments, make 3DMAS as the unstripped gas containing Si, but be not limited to this, can the organic source of amino silicone methane series (BTBAS, 4DMAS, DIPAS) etc. have been used.
And, employ the ozone of oxidizing gas in the above-described embodiments as reactant gases, but be not limited to this, can use from by O
3, O
2, O
2plasma body, N
2the gas of more than selected in group a kind that O, NO are formed, in addition, also can disclosed in Japanese Unexamined Patent Publication 2005-175441 publication, the oxygen activity kind produced under being used in the low pressure of below 133Pa and hydroxyl activity kind.And the shape of processing vessel 22 is only illustrate an example, being not limited to the dual pipe structure illustrated here, can certainly be the processing vessel of single tube structure.
And, semiconductor crystal wafer is illustrated here as handled object, but this semiconductor die fenestra comprises the compound semiconductor substrate such as silicon substrate, GaAs, SiC, GaN, and being not limited to aforesaid substrate, the present invention also can be applicable to the glass substrate, ceramic substrate etc. of liquid crystal indicator.
The advantage added and distortion are easy understand for a person skilled in the art.Thus, the present invention with more embodiment is not limited to shown concrete embodiment, the concrete detailed construction recorded here.Thus, various change can be carried out under the scope of general inventive concept not departing from claims and identity file defined thereof or the prerequisite of spirit.
The application is No. 2010-170758, the Japanese patent application and 2011-105146 CLAIM OF PRIORITY that propose respectively to the Japanese Patent Room based on July 29th, 2010 and on May 10th, 2011, quotes its full content at this.
Claims (14)
1. a film, use film deposition system on handled object, form the film be made up of silicon oxide film, the surface of this handled object is formed with the film containing metal, and this film deposition system comprises:
Processing vessel, it can accommodate above-mentioned handled object;
Unstripped gas plenum system, it has the 1st open and close valve, can to base feed gas in above-mentioned processing vessel;
Reactant gases plenum system, it has the 2nd open and close valve, can to supply response gas in above-mentioned processing vessel;
Vacuum evacuating system, it has the 3rd open and close valve, the atmosphere in above-mentioned processing vessel can be lined up vacuum,
It is characterized in that,
Off period ground alternate repetition repeatedly this absorption process and reaction process is there is between absorption process and reaction process,
This absorption process is, close above-mentioned 3rd open and close valve of above-mentioned vacuum evacuating system, open above-mentioned 1st open and close valve the 1st specified time limit of above-mentioned raw materials gas supply system, after above-mentioned processing vessel supply above-mentioned raw materials gas, close the 1st open and close valve, under the state keeping above-mentioned 1st open and close valve to close for the 2nd specified time limit, make above-mentioned raw materials gas adsorption in above-mentioned processing vessel in the surface of above-mentioned handled object;
This reaction process is, opens above-mentioned 2nd open and close valve of above-mentioned reactant gases plenum system, in above-mentioned processing vessel, supplies above-mentioned reactant gases, make above-mentioned reactant gases and above-mentioned raw materials gas react and form film,
Wherein, the length of above-mentioned 2nd specified time limit of being closed by above-mentioned 1st open and close valve adjusting above-mentioned raw materials gas supply system in above-mentioned absorption process, controls to be formed at the thickness of the metal oxide film of the above-mentioned film containing metal at the interface between above-mentioned film containing metal and above-mentioned film.
2. film according to claim 1, is characterized in that,
Above-mentioned off period carry out opening above-mentioned vacuum evacuating system above-mentioned 3rd open and close valve and to the deairing step be exhausted in above-mentioned processing vessel.
3. film according to claim 2, is characterized in that,
In above-mentioned deairing step, in above-mentioned processing vessel, supply non-active gas.
4. film according to claim 2, is characterized in that,
In above-mentioned deairing step, stop supplying all gas in above-mentioned processing vessel, above-mentioned processing vessel is exhausted.
5. film according to claim 1, is characterized in that,
The length of above-mentioned 2nd specified time limit makes the thickness of the above-mentioned metal oxide film after forming above-mentioned film be the such length of below the initial film thickness of the above-mentioned metal oxide film of self-assembling formation.
6. film according to claim 1, is characterized in that,
Rate of film build in 1 circulation when repeated multiple times above-mentioned absorption process and above-mentioned reaction process is more than or equal to 0.11nm/ circulation.
7. film according to claim 1, is characterized in that,
Above-mentioned raw materials gas is made up of the organic source of amino silicone methane series.
8. film according to claim 7, is characterized in that,
The above-mentioned organic source of amino silicone methane series is SiH (N (CH
3)
2)
3, i.e. 3DMAS, the temperature of the above-mentioned handled object in above-mentioned absorption process and above-mentioned reaction process is more than 550 DEG C.
9. film according to claim 7, is characterized in that,
The above-mentioned organic source of amino silicone methane series is diisopropylaminoethyl silane, i.e. DIPAS, and the temperature of the above-mentioned handled object in above-mentioned absorption process and above-mentioned reaction process is less than 450 DEG C.
10. film according to claim 1, is characterized in that,
The above-mentioned film containing metal is from a kind of film selected in the group be made up of tungsten film, tungsten nitride film, titanium film, titanium nitride film, tantalum film and nitrogenize tantalum film.
11. films according to claim 1, is characterized in that,
Above-mentioned raw materials gas is formed by utilizing gasifier to make liquid starting material gasify.
12. films according to claim 11, is characterized in that,
Above-mentioned gasifier comprises material container, and this material container, for adjusting the vapour pressure determined by the temperature of aforesaid liquid raw material, controls the amount of the raw material that will gasify.
13. films according to claim 1, is characterized in that,
Above-mentioned reactant gases is by from by O
3, O
2, N
2the gas of more than selected in group a kind that O, NO are formed is formed.
14. 1 kinds of film deposition systems, is characterized in that,
This film deposition system comprises:
Processing vessel, it can accommodate handled object;
Maintaining part, it is for keeping above-mentioned handled object;
Heating part, it is for heating above-mentioned handled object;
Unstripped gas plenum system, it has the 1st open and close valve, can to base feed gas in above-mentioned processing vessel;
Reactant gases plenum system, it has the 2nd open and close valve, can to supply response gas in above-mentioned processing vessel;
Vacuum evacuating system, it has the 3rd open and close valve, the atmosphere in above-mentioned processing vessel can be lined up vacuum;
Apparatus control portion, it makes the film described in the overall enforcement of rights requirement 1 of this device for control device entirety.
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| JP2010170758 | 2010-07-29 | ||
| JP2010-170758 | 2010-07-29 | ||
| JP2011-105146 | 2011-05-10 | ||
| JP2011105146A JP5541223B2 (en) | 2010-07-29 | 2011-05-10 | Film forming method and film forming apparatus |
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| CN102345111B true CN102345111B (en) | 2015-03-04 |
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| CN108690954B (en) * | 2017-04-10 | 2021-03-23 | 株式会社新柯隆 | Film forming apparatus and film forming method |
| JP6807275B2 (en) * | 2017-05-18 | 2021-01-06 | 東京エレクトロン株式会社 | Film formation method and film deposition equipment |
| JP7203670B2 (en) * | 2019-04-01 | 2023-01-13 | 東京エレクトロン株式会社 | Film forming method and film forming apparatus |
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| CN1624194A (en) * | 2003-11-13 | 2005-06-08 | 波克股份有限公司 | Atomic layer deposition process and apparatus |
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| JP2009246318A (en) * | 2008-04-01 | 2009-10-22 | Hitachi Kokusai Electric Inc | Film forming method |
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| KR20030081144A (en) * | 2002-04-11 | 2003-10-17 | 가부시키가이샤 히다치 고쿠사이 덴키 | Vertical semiconductor manufacturing apparatus |
| JP2006245089A (en) * | 2005-03-01 | 2006-09-14 | Mitsui Eng & Shipbuild Co Ltd | Method for forming thin film |
| JP4711733B2 (en) * | 2005-05-12 | 2011-06-29 | 株式会社Ａｄｅｋａ | Method for producing silicon oxide thin film |
| JP4836761B2 (en) * | 2006-11-29 | 2011-12-14 | 株式会社日立国際電気 | Manufacturing method of semiconductor device |
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| CN1624194A (en) * | 2003-11-13 | 2005-06-08 | 波克股份有限公司 | Atomic layer deposition process and apparatus |
| CN100426475C (en) * | 2004-07-15 | 2008-10-15 | 东京毅力科创株式会社 | Method and apparatus for forming silicon oxide film |
| CN101378007A (en) * | 2007-08-31 | 2009-03-04 | 东京毅力科创株式会社 | Plasma processing apparatus |
| JP2009246318A (en) * | 2008-04-01 | 2009-10-22 | Hitachi Kokusai Electric Inc | Film forming method |
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