CN101529565A - Method for forming high dielectric film and method for manufacturing semiconductor device - Google Patents

Method for forming high dielectric film and method for manufacturing semiconductor device Download PDF

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Publication number
CN101529565A
CN101529565A CNA200780040077XA CN200780040077A CN101529565A CN 101529565 A CN101529565 A CN 101529565A CN A200780040077X A CNA200780040077X A CN A200780040077XA CN 200780040077 A CN200780040077 A CN 200780040077A CN 101529565 A CN101529565 A CN 101529565A
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high dielectric
dielectric film
semiconductor device
film
manufacture method
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内田博章
高桥毅
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
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Abstract

The present invention discloses a method for forming a high dielectric film, which comprises a step for forming a high dielectric film on a substrate by ALD or CVD using an organic metal raw material at a temperature not more than 350 DEG C, and a step for eliminating hydrogen in the high dielectric film by irradiating the film with ultraviolet light in an oxygen-containing atmosphere at a low pressure.Also disclosed is a method for manufacturing a semiconductor device, which comprises a step for forming a high dielectric film as a gate insulating film on a semiconductor substrate by ALD or CVD using an organic metal raw material at a temperature not more than 350 DEG C, a step for eliminating hydrogen in the high dielectric film by irradiating the film with ultraviolet light in an oxygen-containing atmosphere at a low pressure, and a step for forming a gate electrode on the high dielectric film.

Description

The formation method of high dielectric film and the manufacture method of semiconductor device
Technical field
The present invention relates to be applicable to gate insulating film in the semiconductor device, capacitor films high dielectric film the formation method and use the manufacture method of the semiconductor device of this high dielectric film.
Background technology
In recent years, the requirement according to highly integrated, the high speed of LSI constitutes the continuous miniaturization of design rule of the semiconductor element of LSI, and thereupon, in cmos device, gate insulating film is required it is with SiO 2The following value of 1.5nm degree of the EOT of electric capacity conversion thickness (Equivalent Oxide Thickness, equivalent oxide thickness) expression.Realize the material of thin like this dielectric film as not increasing grid leakage current ground, high dielectric constant material, so-called High-k material receive publicity.
With high dielectric constant material as under the situation of gate insulating film, need its not with the counterdiffusion mutually of silicon substrate, stable aspect thermodynamics, from this viewpoint, the oxide of hafnium, zirconium or its metal silicate are considered to very promising.
As the film build method of such high dielectric film, known use organo metallic material carries out chemical vapor deposition (CVD) method of film forming, carries out the method (for example TOHKEMY 2004-079753 (patent documentation 1)) of film forming by atomic layer evaporation (ALD) method of alternative supply raw metal gas and oxidant as raw metal gas.And, after such film forming, carry out nitrogen according to demand and add operation, annealing operation etc., thereby can form the high dielectric gate insulating film.
But, forming according to these methods under the situation of high dielectric films, from doing one's utmost to avoid dysgenic viewpoint, trend towards under the condition of low temperature more, forming film to device.On the other hand, contain a large amount of hydrogen in the organic metal raw material, and, also use the gas that contains hydrogen as oxidant, in the process that makes the oxidation of organic metal raw material, generate hydrogeneous composition.If so hydrogeneous composition enters in the film, then under the condition of low temperature, be difficult to from film, discharge, remain in the film easily.If so hydrogeneous composition remains in the film, then when forming semiconductor device (transistor), can cause generation, the Vth skew of interfacial state (interface state), the reliability of infringement device.
Summary of the invention
Even the object of the present invention is to provide a kind of the use under the film formation at low temp condition of organo metallic material, also be difficult to the formation method of the high dielectric film of residual hydrogeneous composition in film.
Another object of the present invention is to provide a kind of manufacture method of semiconductor device of the manufacture method of using such high dielectric film.
Further, another object of the present invention is to provide a kind of storage medium that stores the program of the formation method that is used to carry out such high dielectric film.
According to first viewpoint of the present invention, a kind of formation method of high dielectric film is provided, it comprises: using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With the operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to above-mentioned high dielectric film irradiation ultraviolet radiation.
According to second viewpoint of the present invention, a kind of manufacture method of semiconductor device is provided, this semiconductor device has high dielectric film as gate insulating film or capacitor films, and above-mentioned high dielectric film forms by the method with following operation: using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With the operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to above-mentioned high dielectric film irradiation ultraviolet radiation.
According to the 3rd viewpoint of the present invention, a kind of manufacture method of semiconductor device is provided, it comprises: using the organic metal raw material to form operation as the high dielectric film of gate insulating film with the temperature below 350 ℃ by ALD or CVD on the semiconductor substrate; The operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to above-mentioned high dielectric film irradiation ultraviolet radiation; With the operation that on above-mentioned high dielectric film, forms gate electrode.
In above-mentioned first～the 3rd viewpoint,, can use oxide or the silicate of Hf or Zr as above-mentioned high dielectric film.In this case, can use the amide-type metallic compound as above-mentioned organic metal raw material.When forming high dielectric film, can use H 2O is as oxidant.
In addition, above-mentioned ultraviolet irradiation preferably carries out under the pressure of 0.665～665Pa.Above-mentioned ultraviolet irradiation preferably carries out under the state that substrate is heated to the temperature below 500 ℃.Above-mentioned ultraviolet irradiation can be at O 2Carry out in the gas atmosphere.Above-mentioned ultraviolet irradiation can use wavelength to carry out as the ultraviolet ray of 172nm.
According to the 4th viewpoint of the present invention, a kind of storage medium is provided, it stores in computer and carries out, the program of the formation device of control high dielectric film, said procedure is when carrying out, in the mode of the formation method of carrying out high dielectric film, make the formation device of the above-mentioned high dielectric film of computer control, the formation method of above-mentioned high dielectric film comprises: using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With the operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to above-mentioned high dielectric film irradiation ultraviolet radiation.
According to the present invention, after hydrogeneous composition remains in the film forming of high dielectric film in the film, that use organic metal raw material is undertaken by ALD or CVD with the condition below 350 ℃ easily, in the ultraviolet irradiation of carrying out under the low pressure condition in oxygen-containing gas atmosphere, thereby hydrogen is broken away from from high dielectric film, can prevent to remain in the reduction of the reliability of the device that causes in the film owing to hydrogeneous composition.
The technology of irradiation ultraviolet radiation is disclosed in Japanese kokai publication hei 9-121035 communique when forming high dielectric film by the ALD method.But, in this communique, in the disclosed technology, hocket at O 3Ultraviolet irradiation (the UV-O that carries out in the atmosphere 3Annealing) and high dielectric film form, form the high dielectric film of specific thickness, thus oxygen disappearance that can repair membrane, thereby its with after the formation high dielectric film, carry out ultraviolet irradiation breaks away from hydrogen from film the present invention and have significantly different.Therefore, in the technology of Japanese kokai publication hei 9-121035 communique, in order to keep the O that is used to repair the oxygen disappearance 3Concentration need under high pressure carry out UV-O 3Annealing, and in the present invention, break away from the oxygen-containing gas atmosphere that forms low pressure in order to make hydrogen.
Though the mechanism that breaks away from about the hydrogen among the present invention is also not exclusively clear and definite, can infer that its reason is, the key by hydrogen atom such as ultraviolet irradiation cut-out C-H and other atoms utilizes oxygen-containing gas to repair this part.
Description of drawings
Fig. 1 is the flow chart of operation of an execution mode that is used to illustrate the formation method of high dielectric film of the present invention.
Fig. 2 A is the operation sectional view of operation of an execution mode that is used to illustrate the formation method of high dielectric film of the present invention.
Fig. 2 B is the operation sectional view of operation of an execution mode that is used to illustrate the formation method of high dielectric film of the present invention.
Fig. 3 is illustrated in residual after the film forming high dielectric film of state of hydrogen to be arranged as gate insulating film, and form gate electrode thereon, when carrying out necessary processing formation MOS type device thereafter, measure the result's who asks for Vfb skew gained figure by Vstress.
Fig. 4 is that the high dielectric film of the formation method of the expression high dielectric film that is used to implement present embodiment forms schematic representation of apparatus.
Fig. 5 A is the vertical cross-section diagram that is illustrated in the ultraviolet irradiation unit of carrying on the high dielectric membrane formation device of Fig. 4.
Fig. 5 B is the horizontal sectional view that is illustrated in the ultraviolet irradiation unit of carrying on the high dielectric membrane formation device of Fig. 4.
Fig. 6 A is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 6 B is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 6 C is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 6 D is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 6 E is the operation sectional view of Production Example of the mos semiconductor device of the expression method of using present embodiment.
Fig. 7 A is the figure that is illustrated in the result of the hydrogen concentration gained of measuring film under the situation of carrying out ultraviolet irradiation after the film forming of HfO film.
Fig. 7 B is the figure that is illustrated in the result of the hydrogen concentration gained of measuring film under the situation of not carrying out ultraviolet irradiation after the film forming of HfO film.
Embodiment
Below, with reference to accompanying drawing embodiments of the present invention are carried out specific description.
Fig. 1 is the flow chart of operation of an execution mode that is used to illustrate the formation method of high dielectric film of the present invention.Fig. 2 A, Fig. 2 B are the operation sectional views of this moment.
This method has: the operation (STEP1, Fig. 2 A) that forms high dielectric film 2 on substrate 1; With high dielectric film 2 is remained in the low pressure atmosphere and the operation (STEP2, Fig. 2 B) of irradiation ultraviolet radiation (UV) 3.
As by STEP1 by the material of the high dielectric film 2 of film forming, can exemplify various materials, above-mentioned hafnium, the oxide of zirconium or its metal silicate, i.e. HfO 2, ZrO 2, HfSiO xDeng certainly, can also enumerate SrTiO in addition x, La 2O 3, Y 2O 3
High dielectric film 2 carries out film forming by ALD or the CVD that uses the organic metal raw material with the temperature below 350 ℃.Use the organic metal raw material, utilize ALD or CVD, make temperature, thereby in device, use under the situation of the low material of thermal endurance such as NiSi, also can not be adversely affected below 350 ℃.Be preferably film temperature below 300 ℃.
Organic metal raw material as the film forming that is used to carry out above-mentioned material, can exemplify out TEMAH (テ ト ラ エ ト キ ス メ テ Le エ チ Le ア ミ De Ha Off ニ ウ system, four (ethyl dimethylamine base) hafnium), TDEAH (テ ト ラ ジ エ チ Le ア ミ De Ha Off ニ ウ system, four (diethylin) hafnium) and TEMAZ (テ ト ラ エ ト キ ス メ テ Le エ チ Le ア ミ De ジ Le コ ニ ウ system, four (ethyl dimethylamine base) zirconium) etc.
In addition, when these organic metal raw materials being carried out oxidation and form above-mentioned high dielectric film 2, can enumerate H as oxidant 2O, O 3, O 2, NO 2, N 2O, NO etc.Wherein, preferred H 2O is because it can and then reduce the residual carbon in the film.
When using these organic metal raw materials and oxidant and forming high dielectric film by ALD, on the pedestal of substrate-placing in being arranged on chamber, make and be specified vacuum atmosphere in the chamber, substrate is heated to the temperature of the regulation below 350 ℃, and, at first in chamber according to the rules flow supply with the organic metal raw material, make it to be adsorbed on the substrate, afterwards, flow is supplied with oxidant according to the rules, makes adsorbed organic metal raw material oxidation, forms the high dielectric film of 1～number molecular layer degree, alternate repetition carries out above-mentioned operation, forms the high-k films of desirable thickness.
In addition, using these organic metal raw materials and oxidant and forming by CVD under the situation of high dielectric film, on the pedestal of substrate-placing in being arranged on chamber, and substrate is heated to the temperature of the regulation below 350 ℃, and, supply with organic metal raw material and oxidant simultaneously, form the high-k films of desirable thickness.
Above-mentioned ALD utilizes oxidant to make it oxidation after the organic metal raw material film that is adsorbed with as thin as a wafer, so it is reactive high, compares with CVD, can carry out film forming at low temperatures.Therefore, in order to implement the more preferred ALD of film forming of low temperature.
But, forming under the situation of high dielectric film by ALD or CVD like this, owing to contain a large amount of hydrogen in the organic metal raw material, so residual hydrogeneous composition in film easily, and, because film-forming temperature is below 350 ℃, be low temperature, so hydrogen is difficult to break away from from residual hydrogeneous composition.Therefore, if will in semiconductor device, use, then, cause generation, the Vth skew of interfacial state owing to remain in hydrogen in the film by the high dielectric film former state ground that such method is carried out the state after the film forming.For example, at the high dielectric film of the state that hydrogen is arranged with residual after the film forming as gate insulating film, and form gate electrode thereon, when carrying out necessary processing formation MOS type device thereafter, measure the result who asks for Vfb skew gained by Vstress, as shown in Figure 3, can confirm that Δ Vfb can reach 1.0V.
Therefore, in the present embodiment, after under the condition of easy residual hydrogeneous composition, forming high dielectric film as mentioned above, carry out the ultraviolet irradiation operation as STEP2.The ultraviolet irradiation operation of this STEP2 is carried out in the oxygen-containing atmosphere of low pressure condition.Like this, by the UV treatment with irradiation of low pressure, the hydrogen in the high dielectric film is broken away from.That is, can infer,, can cut off the hydrogen in the hydrogeneous composition and the key of other elements, thereby Hydrogen Energy break away from enough by the ultraviolet irradiation under the low pressure.Here, so-called low pressure is the enough low pressure of the degree that enough breaks away from of Hydrogen Energy.That is, the hydrogen in the high dielectric film under low pressure breaks away from when ultraviolet irradiation easily, therefore, carries out ultraviolet irradiation in low pressure atmosphere.Specifically, pressure is preferably below the 665Pa.In addition, the atmosphere during ultraviolet irradiation is oxygen-containing atmosphere, for example O 2Gas atmosphere.This be because, to O 2The gas irradiation ultraviolet radiation produces O 2Free radical also helps the disengaging of carbon when the hydrogen in helping film breaks away from.In addition, Ci Shi temperature is preferably below 500 ℃.This is in order to reduce the heat budget (thermal budget) to the device that forms on substrate.Be preferably below 450 ℃, further preferred below 400 ℃.As the ultraviolet ray of shining, wavelength is preferably about 150～250nm, for example can utilize ultra-violet lamp to shine.In ultraviolet irradiation, can use Xe lamp (wavelength 0.172 μ m).The ultraviolet irradiation time is preferably about tens of seconds degree to 1 minute.
The high dielectric film of Xing Chenging can reduce the residual harmful effect of hydrogen as mentioned above, so, can be applicable to the gate insulating film of mos semiconductor device, the capacitor films of in DRAM etc., using.
Then, the device to the formation method of the high dielectric film that is used to implement present embodiment describes.Fig. 4 is that the high dielectric film of the formation method of the expression high dielectric film that is used to implement present embodiment forms schematic representation of apparatus.
As shown in Figure 4, this high dielectric membrane formation device 10 comprises: the one-tenth film unit 11 that forms high dielectric film by CVD or ALD; To utilizing into film unit 11 by the ultraviolet irradiation unit 12 of the high dielectric film irradiation ultraviolet radiation (UV) of film forming; And can become between film unit 11 and the ultraviolet irradiation unit 12, do not destroy for example carrying room 13 of semiconductor wafer of vacuum ground conveyance substrate 1.Be provided with the transport mechanism 14 that is used for conveyance substrate 1 at carrying room 13.In addition, not shown load locking room is connected with carrying room 13, disposes the box that is equipped with a plurality of substrates in the outside of this load locking room.From box via load locking room with substrate 1 conveyance to carrying room, carry out predetermined process.
This high dielectric membrane formation device 10 has process controller 15, this process controller 15 is by each structural portion of control, the microprocessor (computer) of film unit 11, ultraviolet irradiation unit 12, carrying room 13 and transport mechanism 14 constitute, each structural portion is connected also Be Controlled with this process controller 15.In addition, on process controller 15, be connected with user interface 16, the keyboard of the input operation that this user interface 16 is instructed in order to manage high dielectric membrane formation device 10 by the process management person etc., can show visually that the display etc. of the running status of plasma processing apparatus constitutes.
In addition, be connected with the storage part 17 of the scheme of storing on process controller 15, this scheme is to be used for control program that control by process controller 15 is implemented in the various processing that high dielectric membrane formation device 10 carries out, to be used for carrying out the program of handling according to treatment conditions in each structural portion of high dielectric membrane formation device 10.Scheme is stored in the storage medium in the storage part 17.Storage medium both can be hard disk or semiconductor memory, also can be movably medium such as CDROM, DVD, flash memory.In addition, also can for example suitably transmit from other devices via special circuit.
As required, according to accessing scheme arbitrarily from storage part 17, process controller 15 is carried out, thereby under the control of process controller 15, in high dielectric membrane formation device 10, carried out desirable processing from the indication of user interface 16 etc.
Above-mentioned one-tenth film unit 11 has the common structure that uses in this kind film forming is handled, for example can use disclosed structure in TOHKEMY 2004-079753 communique.
In addition, as above-mentioned ultraviolet irradiation unit 12, can use the structure of in Fig. 5 A, Fig. 5 B, representing.Fig. 5 A is the vertical cross-section diagram of expression ultraviolet irradiation unit 12, and Fig. 5 B is a horizontal sectional view.
This ultraviolet irradiation unit 12 has the chamber 21 of rectangular shaped, in chamber 21 below, be provided with the workbench 22 of mounting substrate 1.The bottom of workbench 22 is more outstanding than the diapire of chamber 21, and workbench 22 can be by being provided with motor 23 rotations thereunder.Between the diapire of chamber 21 and workbench 22, be provided with the sealing mechanism 24 of fluid seal etc., when workbench 22 rotations, also can keep the air-tightness in the chamber 21.In workbench 22, be embedded with heater 25, to these heater 25 power supplies, can substrate 1 be heated to the temperature of regulation via workbench 22 by illustrated power supply never.
In the position relative of the roof of chamber 21, be provided with ultraviolet irradiation 26 with workbench 22.This ultraviolet irradiation 26 is provided with 2 ultra-violet lamps 27 that extend along the Width of chamber 21.Be provided with in the mode corresponding at the roof of chamber 21 with this ultra-violet lamp 27 fenestrate 28, from ultra-violet lamp 27 by window 28 to substrate 1 irradiation ultraviolet radiation.
Side at the relative minor face of the sidewall of chamber 21 is provided with 3 gases and imports parts 29.On these gases importing parts 29, be connected with and supply with for example O of oxygen-containing gas 2The gas supply system 30 of gas imports parts 29 from this gas supply system 30 by gas and supply with oxygen-containing gas in chamber 21, is retained as oxygen-containing atmosphere in the chamber 21.
The opposing party of the minor face of the sidewall of chamber 21, be provided with the exhaust outlet 31 of flat in the corresponding mode of allocation position that imports parts 29 with three gases.Be connected with blast pipe 32 at exhaust outlet 31, on this blast pipe 32, be connected with not shown exhaust apparatus with vacuum pump etc., thus, can be to carrying out vacuum exhaust in the chamber 21.
On the long limit of the sidewall of chamber 21, be provided with to be used to move into and take out of moving into of substrate 1 and take out of mouthfuls 33, this is moved into and takes out of mouthfuls 33 and can pass through gate valve 34 switches.
Utilize the high dielectric membrane formation device 10 that constitutes as mentioned above, in order to handle according to said sequence, at first, never illustrated box by load locking room to the carrying room 13 conveyance substrates 1 that remain vacuum.Then, substrate 1 is moved into into film unit 11 by the transport mechanisms 14 in the carrying room 13, then, ALD by using the organic metal raw material or CVD carry out high dielectric film on substrate 1 with the temperature below 350 ℃ film forming.
After film forming, by transport mechanism 14 with substrate 1 from becoming film unit 11 to ultraviolet irradiation unit 12 conveyances.Specifically, open gate valve 34, take out of mouthfuls 33 substrate 1 moved in the chamber 21 from moving into by transport mechanism 14, and be positioned on the workbench 22.Under this state, make to be the oxygen atmosphere of aforesaid low pressure condition in the chamber 21, make workbench 22 rotations by motor 23, and heat by 25 pairs of substrates 1 of heater.So, from the ultra-violet lamp 27 of ultraviolet irradiation 26 to irradiation ultraviolet radiation on the substrate 1 of workbench 22 rotations.Thus, carry out the disengaging of the hydrogen in the high dielectric film.
At this moment preferred condition is for as mentioned above, after the film forming of carrying out high dielectric film, by carrying out ultraviolet irradiation like this, can carry out the disengaging of the hydrogen in the high dielectric film, can prevent that the reliability that remains in the device that causes in the film owing to hydrogeneous composition from reducing.
Then, with reference to the operation sectional view of Fig. 6 A～Fig. 6 E, the example of the manufacturing of the mos semiconductor device of the method for using present embodiment is described.
At first, prepare to be formed with the Si substrate 100 (Fig. 6 A) of element separated region 101.At this moment, the transistor formation portion 102 of the interarea of Si substrate 100 is formed by Si, SiON, SiO etc.
Then, as mentioned above, use the organic metal raw material to form the gate insulating film 103 (Fig. 6 B) that constitutes by high dielectric film by ALD or CVD with the temperature below 350 ℃.Then, to gate insulating film 103 irradiation ultraviolet radiation in the oxygen-containing atmosphere of low pressure that constitutes by such high dielectric film that forms, make the hydrogen in the gate insulating film 103 break away from (Fig. 6 C).
Afterwards, according to method commonly used, on gate insulating film 103, form gate electrode 104 (Fig. 6 D).That is, for example on whole, form the film of gate electrode material such as polysilicon, carry out plasma etching by the resist film of photoetching technique after will be graphical as mask afterwards, thereby form gate electrode 104 by CVD.Afterwards, utilize the formation of side wall oxide film 105 and ion injection etc., form diffusion of impurities zone 106 (Fig. 6 E), obtain the mos semiconductor device.
Then, the experimental result that obtains being used to confirm effect of the present invention describes.
At first, on the Si substrate,, carry out the film forming of HfO film with the thickness of 10nm as high dielectric film.At this moment, use TEMAH, use H as oxidant as raw material 2O carries out film forming by ALD.Temperature during film forming is 250 ℃, and pressure is 60Pa.Then, the HfO film for such film forming gained carries out ultraviolet irradiation.At this moment, the O of 450 ℃ of formation temperatures, pressure 2.7Pa in chamber 2Gas atmosphere was by Xe lamp (wavelength 172nm) irradiation 1 minute.For the HfO film of such formation, measure remaining hydrogen concentration by SIMS.In order to compare, measure remaining hydrogen concentration too for the HfO film that does not carry out this processing.
This result of expression in Fig. 7 A, Fig. 7 B.Fig. 7 A is the situation of carrying out ultraviolet irradiation, the situation of Fig. 7 B for not carrying out ultraviolet irradiation.As shown in the drawing, can confirm that hydrogen concentration is 2.5 * 10 under the situation of not carrying out ultraviolet irradiation 21Atm/cm 3, become 7.0 * 10 by carrying out ultraviolet irradiation 20Atm/cm 3, be reduced to background level (background level).In addition, for irradiation ultraviolet radiation not and at 400 ℃ O 3The HfO film that has carried out under the atmosphere handling is measured hydrogen concentration similarly, and the result is the hydrogen concentration roughly the same with the situation that does not have ultraviolet irradiation, can confirm thus, and hydrogen breaks away from effect and produced by ultraviolet irradiation.
In addition, the present invention is not limited to above-mentioned execution mode, can carry out various distortion.For example, use ultraviolet radiator for ultraviolet irradiation in the above-mentioned execution mode, still be not limited thereto.In addition, though the example that the high dielectric film that will the method by present embodiment forms is applied to gate insulating film represent, also can be applied to capacitor films, and also can be applied to other purposes certainly.Further, represented to apply the present invention to the situation of semiconductor device in the above-described embodiment, but be not limited thereto, for example, also can be suitable for being that the flat-panel monitor (FPD) of representative forms under the situation of high dielectric film in other substrates such as substrates with liquid crystal watch showing device (LCD) with substrate.
Utilizability on the industry
The present invention is applicable to the gate insulating film of mos semiconductor device, the electric capacity of DRAM The formation of device film.

Claims (25)

1. the formation method of a high dielectric film is characterized in that, comprising:
Using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With
In the oxygen-containing atmosphere of low pressure,, make the operation of the hydrogen disengaging in the film to described high dielectric film irradiation ultraviolet radiation.
2. the formation method of high dielectric film according to claim 1 is characterized in that:
Described high dielectric film is oxide or the silicate of Hf or Zr.
3. the formation method of high dielectric film according to claim 2 is characterized in that:
Described organic metal raw material is the amide-type metallic compound.
4. the formation method of high dielectric film according to claim 1 is characterized in that:
When forming high dielectric film, use H 2O is as oxidant.
5. the formation method of high dielectric film according to claim 1 is characterized in that:
Described ultraviolet irradiation carries out under the pressure of 0.665～665Pa.
6. the formation method of a high dielectric film is characterized in that:
Described ultraviolet irradiation carries out under the state that substrate is heated to the temperature below 500 ℃.
7. the formation method of high dielectric film according to claim 1 is characterized in that:
Described ultraviolet irradiation is at O 2Carry out in the gas atmosphere.
8. the formation method of high dielectric film according to claim 1 is characterized in that:
Described ultraviolet irradiation uses wavelength to carry out as the ultraviolet ray of 172nm.
9. the manufacture method of a semiconductor device, this semiconductor device has high dielectric film as gate insulating film or capacitor films, and the manufacture method of this semiconductor device is characterised in that:
Described high dielectric film forms by the method that comprises following operation:
Using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With
In the oxygen-containing atmosphere of low pressure,, make the operation of the hydrogen disengaging in the film to described high dielectric film irradiation ultraviolet radiation.
10. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described high dielectric film is oxide or the silicate of Hf or Zr.
11. the manufacture method of semiconductor device according to claim 10 is characterized in that:
Described organic metal raw material is the amide-type metallic compound.
12. the manufacture method of semiconductor device according to claim 9 is characterized in that:
When forming described high dielectric film, use H 2O is as oxidant.
13. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described ultraviolet irradiation carries out under the pressure of 0.665～665Pa.
14. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described ultraviolet irradiation carries out under the state that substrate is heated to the temperature below 500 ℃.
15. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described ultraviolet irradiation is at O 2Carry out in the gas atmosphere.
16. the manufacture method of semiconductor device according to claim 9 is characterized in that:
Described ultraviolet irradiation uses wavelength to carry out as the ultraviolet ray of 172nm.
17. the manufacture method of a semiconductor device is characterized in that, comprising:
Using the organic metal raw material to form the operation of high dielectric film by ALD or CVD on the semiconductor substrate as gate insulating film with the temperature below 350 ℃;
In the oxygen-containing atmosphere of low pressure,, make the operation of the hydrogen disengaging in the film to described high dielectric film irradiation ultraviolet radiation; With
On described high dielectric film, form the operation of gate electrode.
18. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described high dielectric film is oxide or the silicate of Hf or Zr.
19. the manufacture method of semiconductor device according to claim 18 is characterized in that:
Described organic metal raw material is the amide-type metallic compound.
20. the manufacture method of semiconductor device according to claim 17 is characterized in that:
When forming described high dielectric film, use H 2O is as oxidant.
21. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described ultraviolet irradiation carries out under the pressure of 0.665～665Pa.
22. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described ultraviolet irradiation carries out under the state that substrate is heated to the temperature below 500 ℃.
23. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described ultraviolet irradiation is at O 2Carry out in the gas atmosphere.
24. the manufacture method of semiconductor device according to claim 17 is characterized in that:
Described ultraviolet irradiation uses wavelength to carry out as the ultraviolet ray of 172nm.
25. a storage medium, it stores in computer and carries out, the program of the formation device of control high dielectric film, it is characterized in that:
Described program in the mode of the formation method of carrying out high dielectric film, makes the formation device of the described high dielectric film of computer control when carrying out, the formation method of described high dielectric film comprises:
Using the organic metal raw material to form the operation of high dielectric film by ALD or CVD with the temperature below 350 ℃ on the substrate; With
The operation that in the oxygen-containing atmosphere of low pressure, the hydrogen in the film is broken away to described high dielectric film irradiation ultraviolet radiation.
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