CN102067291B - Nitrogen radical generator, nitriding treatment apparatus, nitrogen radical generating method, and nitriding treatment method - Google Patents
Nitrogen radical generator, nitriding treatment apparatus, nitrogen radical generating method, and nitriding treatment method Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 132
- 150000002831 nitrogen free-radicals Chemical class 0.000 claims abstract description 103
- 239000000758 substrate Substances 0.000 claims abstract description 68
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 67
- 239000010703 silicon Substances 0.000 claims abstract description 67
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 29
- 229920005591 polysilicon Polymers 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 12
- 150000003254 radicals Chemical class 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 65
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 150000004767 nitrides Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000010494 dissociation reaction Methods 0.000 claims description 5
- 230000005593 dissociations Effects 0.000 claims description 5
- 150000003376 silicon Chemical class 0.000 claims description 3
- 150000002829 nitrogen Chemical class 0.000 claims 1
- 239000005543 nano-size silicon particle Substances 0.000 abstract 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 2
- 238000005549 size reduction Methods 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02321—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer
- H01L21/02329—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of nitrogen
- H01L21/02332—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of nitrogen into an oxide layer, e.g. changing SiO to SiON
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67155—Apparatus for manufacturing or treating in a plurality of work-stations
- H01L21/67207—Apparatus for manufacturing or treating in a plurality of work-stations comprising a chamber adapted to a particular process
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- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Plasma Technology (AREA)
- Electrodes Of Semiconductors (AREA)
- Cold Cathode And The Manufacture (AREA)
Abstract
This invention provides a nitrogen radical generator which generate nitrogen radicals without generating plasma, has a simple structure, and can realize a size reduction. The nitrogen radical generator (100) comprises a polysilicon layer (103) including a nanosilicon layer (104) having one main face (104m), a silicon substrate electrode (102) provided on the other main face (103n) of the polysilicon layer (103), a surface electrode (105) provided on one main face (104m) of the nanosilicon layer (104), a first chamber(101) for housing these elements, a first power supply (109) for applying a positive voltage (V1) to the surface electrode (105), a gas inflow port (107) for allowing a nitrogen gas to flow into the first chamber (101), a nitrogen radical generation space (140) for bringing electrons released from one main face (104m) of the nanosilicon layer (104), upon the application of a positive voltage (V1), into contact with the nitrogen gas to generate nitrogen radicals, and a radical outflow port (108) for allowing the nitrogen radicals to discharge from the first chamber (101).
Description
Technical field
The present invention relates to be applicable to production method and the nitridation treatment method of the nitrogen free radical generator of the nitrogen treatment of substrate, the nitrogen treatment device that comprises this nitrogen free radical generator, nitrogen free radical when manufacturing semiconductor device.
Background technology
Nitride (for example, SiON, Si at gate insulating film that is configured for CMOS transistor etc. etc.
3n
4deng) formation in, mainly adopt at ammonia (NH
3), nitrogen (N
2) etc. in nitrogen unstrpped gas, the nitrogen free radical that makes to produce plasma and obtain contacts with substrate, thereby the superficial layer of substrate is carried out to the plasma processing method (for example,, with reference to Japanese Patent Laid-Open 2001-015507 communique (patent documentation 1)) of nitrogenize.
In above-mentioned plasma processing method, need to be for generation of the high frequency electric source of plasma.In addition, (refer to the ion high-speed impact substrate produced by plasma ionization, thereby substrate is caused to damage for the plasma damage suppressed substrate.Lower same.), need between plasma produces the processing region of zone and substrate, (for example,, with reference to Japanese Patent Laid-Open 2002-299330 communique (patent documentations 2)) such as next doors be set.Therefore, the structure of reactor complexity of plasma processing apparatus, thus cause equipment volume increase, expense to increase.
Patent documentation 1: Japanese Patent Laid-Open 2001-015507 communique
Patent documentation 2: Japanese Patent Laid-Open 2002-299330 communique
Summary of the invention
In order to address the above problem, the object of the invention is to, provide a kind of can produce the nitrogen free radical and do not produce plasma, and can be because of the nitrogen free radical generator of miniaturization simple in structure, the nitrogen treatment device that comprises described nitrogen free radical generator, the production method of nitrogen free radical, and nitridation treatment method.
Nitrogen free radical generator involved in the present invention comprises: polysilicon layer, and this polysilicon layer comprises the nanometer silicon layer with an interarea; The silicon substrate electrode, this silicon substrate electrode is formed on another interarea of polysilicon layer; And surface electrode, this surface electrode is formed on an interarea of nanometer silicon layer.In addition, also comprise: the first chamber, this first chamber is held polysilicon layer, silicon substrate electrode and surface electrode; The first power supply, it is positive voltage that this first power supply effects on surface electrode applies with respect to the silicon substrate electrode; Gas inflow entrance, this gas inflow entrance flows in the first chamber nitrogen; The nitrogen free radical produces space, and this nitrogen free radical produces the electronics of launching from an interarea of nanometer silicon layer when space makes to apply above-mentioned positive voltage and contacts and produce the nitrogen free radical with above-mentioned nitrogen; And the free radical flow export, this free radical flow export makes the nitrogen free radical flow out from the first chamber.
In nitrogen free radical generator involved in the present invention, the first power supply can be made as to the pulse power that produces pulse voltage.In addition, nitrogen free radical generator involved in the present invention also comprises: focusing electrode, and this focusing electrode is contained in the first chamber, relative with surface electrode; And second source, it is positive voltage that this second source applies with respect to surface electrode to focusing electrode.
Nitrogen treatment device involved in the present invention is the film formation device that comprises above-mentioned nitrogen free radical generator and nitrogen treatment device.Here, the nitrogen treatment device comprises: the second chamber; Be contained in the second chamber, for the substrate stage of placement substrate thereon; And substrate is contacted with the nitrogen free radical, and by the superficial layer nitrogenize of substrate, thus the nitrogen treatment space of formation nitride layer.
The production method of nitrogen free radical involved in the present invention comprises: first step, and this first step applies voltage to the polysilicon layer that comprises the nanometer silicon layer with an interarea, from an interarea electron emission of nanometer silicon layer; And second step, this second step makes launched electronics contact with nitrogen, thereby produces the nitrogen free radical.
Nitridation treatment method involved in the present invention comprises: first step, and this first step applies voltage to the polysilicon layer that comprises the nanometer silicon layer with an interarea, from an interarea electron emission of nanometer silicon layer; Second step, this second step makes launched electronics contact with nitrogen, thereby produces the nitrogen free radical; And third step, this third step makes the nitrogen free radical contact with substrate, by the superficial layer nitrogenize of substrate, thereby forms nitride layer.
According to the present invention, can provide a kind of can produce the nitrogen free radical and do not produce plasma, and can be because of the nitrogen free radical generator of miniaturization simple in structure, a kind of nitrogen treatment device that comprises described nitrogen free radical generator, a kind of nitrogen free radical production method, and a kind of nitridation treatment method.
The accompanying drawing explanation
Fig. 1 means the concise and to the point cutaway view of an execution mode of nitrogen free radical generator involved in the present invention.
Fig. 2 means the concise and to the point cutaway view of an execution mode of nitrogen treatment device involved in the present invention.
Fig. 3 means the concise and to the point cutaway view of an execution mode of the nitridation treatment method in the present invention.Here, (a) mean to make nitrogen free radical and the contacted state of substrate, (b) the superficial layer nitrogenize of expression substrate and generate the state of nitride layer.
Label declaration
100 nitrogen free radical generators, 101 first chambers, 102 silicon substrate electrodes, 103 polysilicon layers, 103n, the 104m interarea, 104 nanometer silicon layers, 105 surface electrodes, 106 focusing electrodes, 107 gas inflow entrances, 108 free radical flow exports, 109 first power supplys, 110 second sources, 120 electron production components and parts, 140 nitrogen free radicals produce space, 200 nitrogen treatment devices, 201 second chambers, 202 substrate stages, 204 exhaust outlets, 205 exhaust pumps, 230 substrates, 231 nitride layers, 240 nitrogen treatment spaces, 300 nitrogen treatment devices, the transmit direction of E electronics, the inflow direction of F nitrogen, the outflow direction of Fr nitrogen free radical, V
1, V
2voltage
Embodiment
Execution mode 1
With reference to figure 1, an execution mode of nitrogen free radical generator 100 involved in the present invention comprises: polysilicon layer 103, and this polysilicon layer 103 comprises the nanometer silicon layer 104 with an interarea 104m; Silicon substrate electrode 102, this silicon substrate electrode 102 is formed on another interarea 103n of polysilicon layer 103; And surface electrode 105, this surface electrode 105 is formed on an interarea 104m of nanometer silicon layer 104.Surface electrode 105 ground connection.In addition, in Fig. 1, the size of each several part is not corresponding with actual size.For easy understanding, for example, as the electron production components and parts 120 of major part described larger, polysilicon layer 103, nanometer silicon layer 104, surface electrode 105 and focusing electrode 107 etc. by thicker than actual with describing in addition.
Here, silicon substrate electrode 102 comprises the silicon substrate electrode of conductivity and formed electrode on it.Silicon substrate as conductivity is not particularly limited, and for example, can use resistivity is the following N-shaped monocrystalline silicon substrate of 0.02 Ω cm etc.In addition, be formed at electrode on the silicon substrate of conductivity so long as electric conductor gets final product, be not particularly limited, but be preferably the less metal films of work function such as Al film, Au film, Pt film.
In addition, as polysilicon layer 103, so long as have the material of conductivity, get final product, be not particularly limited, can use such as resistivity is the following N-shaped polysilicon layer of 0.02 Ω cm etc.
In addition, so-called nanometer silicon layer 104, refer to a plurality of average grain diameters be nanoscale (for example, 1～10nm) silicon crystallite is the layer of netted combination, to make at least a portion of polysilicon layer 103 by such as anodic oxidation etc., becoming the Porous shape, then by being utilized oxidation processes such as instant heating method etc. to obtain.Utilize thermal excitation to inject the electronics of nanometer silicon layer 104 accelerated by the electric field that puts on nanometer silicon layer 104, advance to surface electrode 105 and be subject to hardly scattering.The electronics that advances to surface electrode 105 is hot electron, and they are launched through surface electrode 105.Here, the thickness of nanometer silicon layer 104 is not particularly limited, but, from being convenient to the viewpoint of producing, is preferably 0.5～1.5 μ m.
In addition, surface electrode 105 is not particularly limited, but from the viewpoint of abundant covering nanometer silicon layer 104 and be convenient to electronics from an interarea 104m emission of nanometer silicon layer 104 by the viewpoint of surface electrode 105, the metal film that is preferably 5～10nm by thickness is formed.In addition, from viewpoint same as described above, surface electrode 105 is preferably the less metal films of work function such as Al film, Au film.
In addition, the nitrogen free radical generator 100 of present embodiment comprises the first power supply 109, and it is positive voltage V that described the first power supply 109 effects on surface electrodes 105 apply with respect to above-mentioned silicon substrate electrode 102
1.Here, the first power supply 109 is not particularly limited, but, from suppressing the nanometer silicon layer because applying the deteriorated viewpoint of voltage, is preferably the pulse power that produces pulse voltage.
By effects on surface electrode 105, applying with respect to silicon substrate electrode 102 is positive voltage V
1, voltage V
1be applied in polysilicon layer 103 and nanometer silicon layer 104 between silicon substrate electrode 102 and surface electrode 105, from an interarea 104m electron emission of nanometer silicon layer 104.The arrow E of Fig. 1 means the transmit direction of electronics.From the electronics of interarea 104m emission of nanometer silicon layer 104, by surface electrode 105, arrive in the first chambers 101.Thus, because silicon substrate electrode 102, polysilicon layer 103, nanometer silicon layer 104 and surface electrode 105 are for produce the components and parts of electronics by applying voltage, therefore be called as electron production components and parts 120.Described electron production components and parts 120 have can with low-voltage produce the scattered through angles of electronics, electron emission less, to the feature such as the dependence of vacuum degree is less.
In addition, the nitrogen free radical generator 100 of present embodiment comprises: the first chamber 101, and 101 pairs of polysilicon layers 103 of this first chamber, silicon substrate electrode 102 and surface electrode 105 are held; Gas inflow entrance 107, this gas inflow entrance 107 flows in the first chamber 101 nitrogen; The nitrogen free radical produces space 140, and this nitrogen free radical produces space 140 and makes to apply above-mentioned positive voltage V
1the time electronics launched from an interarea 104m of nanometer silicon layer 104 contact with nitrogen and produce the nitrogen free radical; And free radical flow export 108, this free radical flow export 108 makes the nitrogen free radical flow out from the first chamber 101.In Fig. 1, arrow F means the inflow direction of nitrogen, and arrow Fr means the outflow direction of nitrogen free radical.
The nitrogen flowed into from gas inflow entrance 107 is by the top of the surface electrode 105 an interarea 104m who is formed at nanometer silicon layer 104.Now, at effects on surface electrode 105, applying with respect to silicon substrate electrode 102 is positive voltage V
1electronics that Shi Congyi interarea 104m is launched, by surface electrode 105 contacts with above-mentioned nitrogen, the covalent bond of nitrogen molecular is dissociated, thereby produce the nitrogen free radical.As mentioned above, in the nitrogen free radical generator of present embodiment, because the scattered through angles of electron emission is less, therefore electronics contacts with nitrogen and the nitrogen free radical that produces the nitrogen free radical produces the space above the interarea 104m that space 140 is generally nanometer silicon layer 104, the space directly over particularly.
Here, because the dissociation energy of the covalent bond of nitrogen molecular is 9.76eV, therefore, in order to make the electronics covalent bond of nitrogen molecular that contacts and dissociate with nitrogen, thereby produce the nitrogen free radical, electronics must have the above energy of 9.76eV.That is, effects on surface electrode 105 that apply, with respect to silicon substrate electrode 102, be positive voltage V
1must be enough large, so that the energy more than 9.76eV to be provided to electronics.Based on described viewpoint, put on the positive voltage V of surface electrode 105
1more than being preferably the 9.76V of the work function gained that deducts surface electrode 105, the above voltage of 10V for example.For example, in the situation that the Au film is used for to surface electrode 105, because its work function is 5.10eV, therefore, put on the voltage V of surface electrode 105
1more than being preferably 14.86V, for example, more than 15V.
In addition, in the nitrogen free radical generator 100 of present embodiment, as mentioned above, when producing the nitrogen free radical, dependence to the vacuum degree in the first chamber 101 is less, but the viewpoint in the life-span of the nitrogen free radical produced from prolongation, the vacuum degree in the first chamber 101 is more high better.Particularly, the pressure in the first chamber 101 is preferably below 10Torr (1333Pa), more preferably below 1Torr (133Pa).
As mentioned above, the nitrogen free radical generator 100 of present embodiment can produce the nitrogen free radical and not produce plasma, can be because of miniaturization simple in structure.
With reference to figure 1, other execution modes of nitrogen free radical generator 100 involved in the present invention are except the structure of the nitrogen free radical generator of execution mode 1, also comprise: focusing electrode 106, this focusing electrode 106 is contained in the first chamber 101, relative with surface electrode 105; And second source 110, it is positive voltage V that 110 pairs of focusing electrodes 106 of this second source apply with respect to surface electrode 105
2.
Here, so-called focusing electrode 106, refer to for making an interarea 104m emission, the electrode that pass the electron focusing of surface electrode 105 from nanometer silicon layer 104.Focusing electrode 106, so long as metal film gets final product, is not particularly limited.From the viewpoint of the electron focusing that effectively makes to be launched, utilize 110 pairs of focusing electrodes 106 of second source that apply, with respect to surface electrode 105, be positive voltage V
2more than being preferably 100V.
In addition, the distance between focusing electrode 106 and surface electrode 105, from effectively making the viewpoint of launched electron focusing, is preferably below 5mm, from the viewpoint that makes efficiently nitrogen flow into, more than being preferably 1mm.
In addition, second source 110 is not particularly limited, but the viewpoint from remaining electronic stability ground is focused on is preferably the power supply that produces constant voltage.
As mentioned above, the nitrogen free radical generator 100 of present embodiment can produce the nitrogen free radical and not produce plasma, can be because of miniaturization simple in structure.
Execution mode 3
With reference to Fig. 1, an execution mode of the production method of nitrogen free radical involved in the present invention comprises: first step, in this first step, the polysilicon layer 103 that comprises the nanometer silicon layer 104 with an interarea 104m is applied to voltage, from an interarea 104m electron emission of nanometer silicon layer 104; And second step, in this second step, make launched electronics contact with nitrogen, thereby produce the nitrogen free radical.
Here, particularly, the first step of electron emission is as described below.; by the polysilicon layer 103 by comprising the nanometer silicon layer 104 with an interarea 104m, be formed in the formed electron production components and parts 120 of another interarea 103n of surface electrode 105 on an interarea 104m of nanometer silicon layer 104 and polysilicon layer 103; utilize the first power supply 109, it is positive voltage V that effects on surface electrode 105 applies with respect to electrode of substrate 102
1carry out.Here, in order to suppress to cause nanometer silicon layer 104 deteriorated because applying voltage, applying positive voltage V
1the time, preferably apply pulse voltage.
In addition, particularly, the second step that produces the nitrogen free radical is as described below.That is, by making to utilize above-mentioned first step to contact to carry out with the nitrogen from gas inflow entrance 107 inflows from an interarea 104m emission of nanometer silicon layer 104, electronics by surface electrode 105.In Fig. 1, arrow F means the inflow direction of nitrogen, and arrow Fr means the outflow direction of nitrogen free radical.
Here, because the dissociation energy of the covalent bond of nitrogen molecular is 9.76eV, therefore, in order to make the electronics covalent bond of nitrogen molecular that contacts and dissociate with nitrogen, thereby produce the nitrogen free radical, electronics must have the above energy of 9.76eV.That is, effects on surface electrode 105 that apply, with respect to silicon substrate electrode 102, be positive voltage V
1must be enough large, so that the energy more than 9.76eV to be provided to electronics.Based on described viewpoint, put on the positive voltage V of surface electrode 105
1more than being preferably the 9.76V of the work function gained that deducts surface electrode 105, the above voltage of 10V for example.For example, in the situation that the Au film is used for to surface electrode 105, because its work function is 5.10eV, therefore, put on the voltage V of surface electrode 105
1more than being preferably 14.86V, for example, more than 15V.
In addition, in the production method of the nitrogen free radical of present embodiment, because the scattered through angles of electron emission is less, therefore electronics contacts with nitrogen and the nitrogen free radical that produces the nitrogen free radical produces the space above the interarea 104m that space 140 is generally nanometer silicon layer 104, the space directly over particularly.
Execution mode 4
With reference to Fig. 2 and Fig. 3, an execution mode of nitrogen treatment device 300 involved in the present invention comprises nitrogen free radical generator 100 and the nitrogen treatment device 200 of execution mode 1 or 2.Here, nitrogen treatment device 200 comprises: the second chamber 201; Be contained in the second chamber 201, for the substrate stage 202 of placement substrate 230 thereon; And substrate 230 is contacted with the nitrogen free radical, and by the superficial layer nitrogenize of substrate 230, thus the nitrogen treatment space 240 of formation nitride layer 231.In addition, nitrogen free radical generator 100 is connected with nitrogen treatment device 200, make to result from nitrogen free radical that the nitrogen free radical of nitrogen free radical generator 100 produces space 140 by free radical flow export 108, contact with the substrate 230 in the second chamber 201 that is contained in nitrogen treatment device 200.In addition, also dispose for to carrying out exhaust outlet 204 and the exhaust pump 205 of decompression exhaust or vacuum exhaust in the second chamber 201.In addition, in Fig. 2, E means the transmit direction of electronics, and F means the inflow direction of nitrogen, and Fr means the outflow direction of nitrogen free radical.
With reference to Fig. 2 and Fig. 3, in the nitrogen treatment device 300 of present embodiment, the nitrogen free radical produced by nitrogen free radical generator 100 contacts with substrate 230, thereby the superficial layer nitrogenize that makes substrate 230 is to form nitride layer 231.For example, make nitrogen free radical and SiO
2substrate (substrate 230) contacts, thereby makes SiO
2the superficial layer nitrogenize of substrate is to form SiON layer (nitride layer).
In addition, in the nitrogen treatment device 200 of the nitrogen treatment device 300 of present embodiment, from the viewpoint in life-span of extending the nitrogen free radical produced, the vacuum degree in the second chamber 201 is more high better.Particularly, the pressure in the first chamber 201 is preferably below 10Torr (1333Pa), more preferably below 1Torr (133Pa).
Here, if pay close attention to the atom shape nitrogen free radical as a kind of nitrogen free radical, decaying to of the atom shape nitrogen free radical in the space that is 10Torr (1333Pa) in vacuum degree, be 1.0 * 10 at its initial concentration
15cm
-3the time, became 1/100 after 1 second.For example, chamber diameter at the second chamber 201 is 300mm, nitrogen flow is that 1SLM (means to take 1 minute as standard state, flow through the flux unit of 1 liter of gas) situation under, consider the decay of atom shape nitrogen free radical, the distance between the surface of nitrogen free radical generation space 140 and substrate 230 is set to 20～30mm left and right.
As mentioned above, nitrogen free radical generator 100 in the nitrogen treatment device 300 of present embodiment can produce the nitrogen free radical and not produce plasma, this device can be because of miniaturization simple in structure, and can carry out nitrogen treatment to the superficial layer of substrate and it not caused to plasma damage.
Execution mode 5
With reference to Fig. 2 and Fig. 3, nitridation treatment method involved in the present invention comprises: first step, in this first step, the polysilicon layer 103 that comprises the nanometer silicon layer 104 with an interarea 104m is applied to voltage, from an interarea 104m electron emission of nanometer silicon layer 104; Second step, make launched electronics contact with nitrogen in this second step, thereby produce the nitrogen free radical; And third step, in this third step, make the nitrogen free radical contact with substrate 230, by the superficial layer nitrogenize of substrate 230, thereby form nitride layer 231.
The first step of present embodiment is identical with first step and the second step of execution mode 3 respectively with second step.Particularly, the third step of present embodiment is as described below.That is,, with reference to Fig. 2, the nitrogen free radical produced by second step is flowed in the second chamber 201 by free radical flow export 108.In Fig. 2, E means the transmit direction of electronics, and F means the inflow direction of nitrogen, and Fr means the outflow direction of nitrogen free radical.With reference to Fig. 2 and Fig. 3, the nitrogen free radical that flows into the second chamber 201 is contacted with substrate 230, thereby the superficial layer nitrogenize that makes substrate 230 is to form nitride layer 231.For example, make nitrogen free radical and SiO
2substrate (substrate 230) contacts, thereby makes SiO
2the superficial layer nitrogenize of substrate is to form SiON layer (nitride layer).Here, in third step, effectively realize the viewpoint of nitrogen treatment from life-span of extending the nitrogen free radical, be preferably pressure in the second chamber 201 and be 10Torr (1333Pa) and carry out when following, more preferably the pressure in the second chamber 201 is that 1Torr (133Pa) carries out when following.
Should think that the execution mode that disclosed is to mean for example in all fields here, rather than restrictive.Can think that scope of the present invention is not to be meaned by above-mentioned explanation, but, by the Range Representation of claim, comprise the meaning equal with the scope of claim and all changes in scope.
Claims (6)
1. a nitrogen free radical generator, is characterized in that, comprising:
Polysilicon layer (103), this polysilicon layer (103) comprises the nanometer silicon layer (104) with interarea (104m); Silicon substrate electrode (102), this silicon substrate electrode (102) is formed on another interarea (103n) of described polysilicon layer (103); Surface electrode (105), this surface electrode (105) is formed on a described interarea (104m) of described nanometer silicon layer (104);
The first chamber (101), this first chamber (101) is for holding described polysilicon layer (103), described silicon substrate electrode (102) and described surface electrode (105);
The first power supply (109), it is positive voltage that this first power supply (109) applies with respect to described silicon substrate electrode (102) to described surface electrode (105);
Gas inflow entrance (107), this gas inflow entrance (107) flows in described the first chamber (101) nitrogen; The nitrogen free radical produces space (140), and this nitrogen free radical produces the electronics of launching from a described interarea (104m) of described nanometer silicon layer (104) while making to apply described positive voltage in space (140) and contacts to produce the nitrogen free radical with nitrogen; And free radical flow export (108), this free radical flow export (108) makes described nitrogen free radical flow out from described the first chamber (101),
Described positive voltage provides the energy more than the dissociation energy 9.76eV of covalent bond of nitrogen molecular to described electronics.
2. nitrogen free radical generator as claimed in claim 1, is characterized in that,
Described the first power supply (109) is for producing the pulse power of pulse voltage.
3. nitrogen free radical generator as claimed in claim 1, is characterized in that, also comprises:
Focusing electrode (106), this focusing electrode (106) is contained in described the first chamber (101), relative with described surface electrode (105); And
Second source (110), it is positive voltage that this second source (110) applies with respect to described surface electrode (105) to described focusing electrode (106).
4. a nitrogen treatment device, this nitrogen treatment device (300) comprises as claim 1 and it is characterized in that to the described nitrogen free radical of any one of claim 3 generator (100) and nitrogen treatment device (200),
Nitrogen treatment device (200) comprising: second chamber (201) of vacuum degree below 10Torr; Be contained in described the second chamber (201), for the substrate stage (202) of placement substrate (230) thereon; And described substrate (230) is contacted with described nitrogen free radical, and by the superficial layer nitrogenize of described substrate (230), thus the nitrogen treatment space (240) of formation nitride layer.
5. the production method of a nitrogen free radical, is characterized in that, comprising:
First step, apply voltage to the polysilicon layer (103) that comprises the nanometer silicon layer (104) with interarea (104m) in this first step, from a described interarea (104m) electron emission of described nanometer silicon layer (104); And
Second step, make launched described electronics contact with nitrogen in this second step, thereby produce the nitrogen free radical,
Described voltage provides the energy more than the dissociation energy 9.76eV of covalent bond of nitrogen molecular to described electronics.
6. a nitridation treatment method, is characterized in that, comprising:
First step, apply voltage to the polysilicon layer (103) that comprises the nanometer silicon layer (104) with interarea (104m) in this first step, from a described interarea (104m) electron emission of described nanometer silicon layer (104);
Second step, make launched described electronics contact with nitrogen in this second step, thereby produce the nitrogen free radical; And
Third step, make described nitrogen free radical contact with substrate (230) in this third step, by the superficial layer nitrogenize of described substrate (230), thereby form nitride layer,
Described voltage provides the energy more than the dissociation energy 9.76eV of covalent bond of nitrogen molecular to described electronics,
Under the vacuum degree of described third step below 10Torr, carry out.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2008/061483 WO2009157060A1 (en) | 2008-06-24 | 2008-06-24 | Nitrogen radical generator, nitriding treatment apparatus, nitrogen radical generating method, and nitriding treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| CN102067291B true CN102067291B (en) | 2013-05-08 |
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| CN2008801300985A Active CN102067291B (en) | 2008-06-24 | 2008-06-24 | Nitrogen radical generator, nitriding treatment apparatus, nitrogen radical generating method, and nitriding treatment method |
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| Country | Link |
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| JP (1) | JP5276101B2 (en) |
| CN (1) | CN102067291B (en) |
| WO (1) | WO2009157060A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5980999A (en) * | 1995-08-24 | 1999-11-09 | Nagoya University | Method of manufacturing thin film and method for performing precise working by radical control and apparatus for carrying out such methods |
| JP2001015507A (en) * | 1999-06-30 | 2001-01-19 | Toshiba Corp | Formation of silicon oxinitride film |
| CN1372302A (en) * | 2001-02-15 | 2002-10-02 | 安内华股份有限公司 | CVD method |
| CN1783431A (en) * | 2004-12-03 | 2006-06-07 | 东京毅力科创株式会社 | Plasma processing apparatus |
| CN101120437A (en) * | 2005-02-01 | 2008-02-06 | 国立大学法人东北大学 | Dielectric film and method for forming same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3062589B2 (en) * | 1995-08-24 | 2000-07-10 | 名古屋大学長 | Thin film formation method by radical control |
| JPH09279339A (en) * | 1996-04-11 | 1997-10-28 | Sony Corp | Sputtering device |
| JP2003086576A (en) * | 2001-09-11 | 2003-03-20 | Hitachi Kokusai Electric Inc | Substrate processing equipment |
| JP4252749B2 (en) * | 2001-12-13 | 2009-04-08 | 忠弘 大見 | Substrate processing method and substrate processing apparatus |
| JP5028593B2 (en) * | 2005-09-30 | 2012-09-19 | 国立大学法人名古屋大学 | Method for producing transparent conductive film |
| JP4963923B2 (en) * | 2006-10-06 | 2012-06-27 | 日本碍子株式会社 | Surface reformer |
| JP5024667B2 (en) * | 2007-06-20 | 2012-09-12 | 国立大学法人名古屋大学 | Radical generator |
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- 2008-06-24 JP JP2010517617A patent/JP5276101B2/en not_active Expired - Fee Related
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5980999A (en) * | 1995-08-24 | 1999-11-09 | Nagoya University | Method of manufacturing thin film and method for performing precise working by radical control and apparatus for carrying out such methods |
| JP2001015507A (en) * | 1999-06-30 | 2001-01-19 | Toshiba Corp | Formation of silicon oxinitride film |
| CN1372302A (en) * | 2001-02-15 | 2002-10-02 | 安内华股份有限公司 | CVD method |
| CN1783431A (en) * | 2004-12-03 | 2006-06-07 | 东京毅力科创株式会社 | Plasma processing apparatus |
| CN101120437A (en) * | 2005-02-01 | 2008-02-06 | 国立大学法人东北大学 | Dielectric film and method for forming same |
Also Published As
| Publication number | Publication date |
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| WO2009157060A1 (en) | 2009-12-30 |
| JP5276101B2 (en) | 2013-08-28 |
| JPWO2009157060A1 (en) | 2011-12-01 |
| CN102067291A (en) | 2011-05-18 |
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