CN101125659A - Diethylsilane as a silicon source in the deposition of metal silicate films - Google Patents

Diethylsilane as a silicon source in the deposition of metal silicate films Download PDF

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CN101125659A
CN101125659A CNA2007101288016A CN200710128801A CN101125659A CN 101125659 A CN101125659 A CN 101125659A CN A2007101288016 A CNA2007101288016 A CN A2007101288016A CN 200710128801 A CN200710128801 A CN 200710128801A CN 101125659 A CN101125659 A CN 101125659A
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Prior art keywords
diethylsilane
reaction zone
metal
silicate
oxygen
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R·D·克拉克
K·S·库特希尔
H·思里丹达姆
A·K·霍克伯格
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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Abstract

A method for forming a metal silicate as a high k dielectric in an electronic device comprises the steps of: providing diethylsilane to a reaction zone; concurrently providing a source of oxygen to the reaction zone; concurrently providing a metal precursor to the reaction zone; reacting the diethylsilane, source of oxygen and metal precursor by chemical vapor deposition to form a metal silicate on a substrate comprising the electronic device. The metal is preferably hafnium, zirconium or mixtures thereof. The dielectric constant of the metal silicate film can be tuned based upon the relative atomic concentration of metal, silicon, and oxygen in the film.

Description

Diethylsilane is as the silicon source of metal refining silicate films
The cross reference of related application
The application requires the rights and interests of the U.S. Provisional Patent Application sequence number 60/809,255 of application on May 30th, 2006.
Technical field
The application relates to the method that forms as the metal silicate of high-k dielectric.
Background technology
The electronics process industry is used the metal silicate film of zirconium or hafnium in electron device is made, for example as high dielectric constant material and grid dielectric film.
The metal silicate that is used for electronic material was studied by those skilled in the art.For example, people's such as Wilk Hafnium and Zirconium silicates for advanced gate dielectrics, Journal of AppliedPhysics, the 87th volume, No.1,2000, the 484-492 pages or leaves have been described and have been used metal silicate as the grid dielectric film with different metal content.Deposition is undertaken by sputter and electron beam evaporation.The specified temp deposition barrier film of in 25 ℃ to 600 ℃, selecting.
US6841439 determines metal silicate as required grid dielectric film, and has described different route of synthesis.
The open date of U.S. Patent Application Publication No.2005/0139937A1: on June 30th, 2005, description is by the ald hafnium silicate film of growing, and described ald is a kind of by alternately hafnium, silicon and oxygen source are supplied to deposit cavity and with its technology of clearing out from deposit cavity.The growth velocity of atom layer deposition process is very low.
The present invention has overcome this defective by side by side supply with metal, silicon and oxygen source in chemical vapour deposition to deposit cavity.
Summary of the invention
A kind of embodiment of the present invention is to form the method for metal silicate as high-k dielectric in electron device, comprises step: provide diethylsilane to reaction zone; Provide oxygen source to arrive this reaction zone simultaneously; Provide metal precursor to arrive this reaction zone simultaneously; By chemical vapour deposition diethylsilane, oxygen source and metal precursor are reacted, on substrate, to form metal silicate.
Another embodiment of the present invention is to form the method for hafnium silicate as high-k dielectric in electron device, comprises step:
Provide diethylsilane to reaction zone;
Provide oxygen source to arrive this reaction zone simultaneously;
Provide four (diethylin) hafnium to this reaction zone simultaneously;
By chemical vapour deposition diethylsilane, oxygen source and four (diethylin) hafnium are reacted, to form hafnium silicate comprising on the substrate of this electron device.
Another embodiment of the present invention is to form the method for zirconium silicate as high-k dielectric in electron device, comprises step:
Provide diethylsilane to reaction zone;
Provide oxygen source to arrive this reaction zone simultaneously;
Provide four (diethylin) zirconium to this reaction zone simultaneously;
By chemical vapour deposition diethylsilane, oxygen source and four (diethylin) zirconium are reacted, to form zirconium silicate comprising on the substrate of this electron device.
The present invention shows that also the specific inductivity of metal silicate film can regulate based on the corresponding atomic percent of metal, silicon and oxygen in the film.
Description of drawings
Fig. 1 shows that absorbancy is as the wave number (cm by following sedimentary film -1) function: separately by Zr (N (CH 2CH 3) 2) 4Zirconium oxide film-the V1519 that generates, the silicon oxide film-V1522 that generates by diethylsilane separately, and by Zr (N (CH 2CH 3) 2) 4Zirconium silicate film-V1525 with the diethylsilane generation; According to Table III.
Fig. 2 shows that the specific refractory power of Hf-Si-O film is as SiH 2(CH 2CH 3) 2The function of flow velocity (sccm); According to Table V.
Embodiment
The present invention relates to form metal silicate as the electron device high-k dielectric.In chemical vapour deposition, supply with metal, silicon and oxygen source simultaneously to deposit cavity.In the middle of the silicon source, select diethylsilane for use in the deposition of metal silicate film of the present invention.The growth velocity of metal silicate is faster than the growth velocity that realizes by ald.Compare with technology demonstration (US6537613 (being incorporated herein by reference in full with it especially here thus), it uses silicon acid amides (silicon amide) as the silicon source) with we are report before, find that the Prevent Carbon Contamination in the metal silicate film is lower.Low Prevent Carbon Contamination causes higher dielectric constant.Another advantage be incorporated in these films silicon can with use the silicon acid amides to compare under lower technological temperature to obtain as the technology in silicon source; Reduced the budget (and therefore reducing the technology cost) of thermal treatment process.Most important ground, the present invention has also disclosed the specific inductivity of metal silicate film and can regulate based on the atomic percent of metal, silicon and oxygen in the film.
Configuration chemical vapor deposition (CVD) system with accept simultaneously by direct liquid inject metal precursor that (DLI) (being converted into steam in the past at reaction zone) supply with, the silicon precursor steam of supplying with by steam extraction device (Vapor Draw) and the oxygen reactant gas that supplies to reaction zone on the heated substrate.Determine the temperature and pressure of reaction zone; And before being incorporated into reaction zone, determine precursor vapor and reactant gas flow.Substrate is introduced in reaction zone, and the temperature and pressure equilibrium in homologation reaction district.Introduce precursor vapor and reactant gas and flow to reaction zone, and allow that for some time of flowing is with enough growing metal silicate films.
Operational conditions is: pressure is 0.5 to 2 holder; Underlayer temperature is 250 ℃-450 ℃; The DLI evaporator temperature is 85 ℃-95 ℃; The metal precursor flow velocity is 0.05 to 0.1ml/min; The helium carrier gas flow velocity is 100 to 150sccm (standard cubic centimeter per minute); The silicon precursor flow velocity is 5 to 100sccm; The HD gas flow rate is 0 to 50sccm; Residence time is 0.05 to 2 second.
Work embodiment
Introduce the present invention among the embodiment below.
Embodiment 1 Zr-Si-O film
The reactant that uses in the Zr-Si-O thin film deposition is:
1) four (diethylin) zirconium (IV)-TDEAZ, Zr (N (CH 2CH 3) 2) 4
2) diethylsilane-DES (LTO-410), SiH 2(CH 2CH 3) 2With
3) oxygen, O 2
Liquid four (diethylin) zirconium (IV) is delivered to direct liquid injection system with the 0.1mL per minute, under 90 ℃ of temperature, evaporate subsequently, this evaporation uses the helium cleaned gas stream of 100sccm to clean in the manifold, this manifold is sent ring to presoma and is carried out charging, and this presoma is sent the bottom that ring is positioned at the gas jet (gas showerhead) of single wafer cold wall LPCVD reactor.Nitrogen mass flow controller (MFC) (equaling the diethylsilane of 18sccm full scale (full scale) flow) by 100sccm with the flow velocity of 6.3sccm side by side with the diethylsilane steam delivery to foregoing manifold.The Oxygen Flow that changes between 100sccm and 150sccm is delivered to the nozzle of reactor.These three kinds of streams are directed into simultaneously on the silicon wafer of the temperature maintenance on the heat-resisting wafer base 250 ℃ and 450 ℃.Reactor cavity pressure changes between 1 holder and 1.5 holders.
Table I illustrates deposition by Zr (N (CH 2CH 3) 2) 4And O 2The ZrO that generates 2The needed processing parameter of film; " only TDEAZ ".
Table II illustrates deposition by SiH 2(CH 2CH 3) 2And O 2The SiO that generates 2The needed processing parameter of film; " only DES ".
Table III illustrates by sending Zr (N (CH simultaneously 2CH 3) 2) 4, SiH 2(CH 2CH 3) 2And O 2To the needed processing parameter of reactor cavity deposition Zr-Si-O film; " TDEAZ and DES ".
As shown in Table I, ZrO 2Film obtains high deposition rate and high refractive index.
As shown in Table II, SiO 2Film obtains relatively low specific refractory power.Sedimentation rate changes.
Table III shows the relatively low sedimentation rate of zirconium silicate film.The refractive index ratio SiO of Zr-Si-O film 2The specific refractory power of film is much higher, like this specific inductivity k height of Zr-Si-O film.
Table I is TDEAZ only
Curve Chip temperature (℃) Pressure (millitorr) DLI (ml/min) HeSwp (sccm) DES (sccm) O 2; (sccm) Working time (min) Refractive index n Thickness () Sedimentation rate (/min)
V1519 296 1000 0.1 100 0 100 2.5 2.146 2618 1047
V1520 316 1000 0.1 100 0 100 1.2 2.143 1857 1592
V1521 277 1000 0.1 100 0 100 3.5 2.092 2412 689
Table II is DES only
Curve Chip temperature (℃) Pressure (millitorr) DLI (ml/min) HeSwp (sccm) DES (sccm) O 2; (sccm) Working time (min) Refractive index n Thickness () Sedimentation rate (/min)
V1522 400 Variable 0 0 Variable 100 na 1.444 Variable Variable
Table III TDEAZ and DES
Curve Chip temperature (℃) Pressure (millitorr) DLI(ml/min) HeSwp (sccm) DES (sccm) O 2; (sccm) Working time (min) Refractive index n Thickness () Sedimentation rate (/min)
Inject DES by ring
V1525 405 1500 0.1 100 6.3 100 1.5 1.942 923 615
V1526 405 1500 0.1 150 6.3 100 1.5 1.882 931 621
V1527 405 1500 0.1 100 6.3 150 2 1.711 606 303
Fig. 1 shows ZrO 2, SiO 2With each FTIR spectrum of Zr-Si-O film, described spectrum is stacked mutually.Curve V1519 is ZrO 2Spectrum.The absorption at 1545 wave number places represents that Zr-O-Zr is flexible.Curve V1522 is SiO 2The spectrum of film.Absorption at 1074 wave number places is the flexible eigenwert of Si-O-Si.Curve V1525 is the spectrum of Zr-Si-O film; It demonstrates the characteristic peak of two independent oxide compounds simultaneously, and the eigenwert of Zr-Si-O film promptly is shown.
Embodiment 2 Hf-Si-O films
The similar test of carrying out as shown in Example 1 forms the Hf-Si-O film.Notice that because they belong to the same gang in the periodictable, the chemical property of hafnium and zirconium is closely similar.
The reactant that uses in the Hf-Si-O thin film deposition is:
1) four (diethylin) hafnium (IV)-TDEAH, Hf (N (CH 2CH 3) 2) 4
2) diethylsilane-DES (LTO-410), SiH 2(CH 2CH 3) 2With
3) oxygen, O 2
Liquid four (diethylin) hafnium (IV) is delivered to direct liquid injection system with the 0.1mL per minute, under 90 ℃ of temperature, evaporate subsequently, this evaporation uses the helium cleaned gas stream of 100sccm to clean in the manifold, this manifold is sent ring to presoma and is carried out charging, and this presoma is sent the bottom that ring is arranged in the gas jet of single wafer cold wall LPCVD reactor.Nitrogen MFC by 500sccm with the flow velocity (equaling 90sccm diethylsilane full scale flow) of 6.3sccm to 45sccm side by side with the diethylsilane steam delivery in foregoing manifold.The Oxygen Flow that changes between 75sccm and 100sccm is delivered to the nozzle of this reactor.These three kinds of streams are directed to simultaneously on the silicon wafer that maintains the well heater design temperature on the heat-resisting wafer base, and described well heater design temperature is 650 ℃ to 700 ℃.Reaction chamber air pressure changes between 0.5 holder and 1.5 holders.
Table IV illustrates deposition by Hf (N (CH 2CH 3) 2) 4And O 2The HfO that generates 2The needed processing parameter of film; " only TDEAH ".
Table IV is TDEAH only
Curve Chip temperature (℃) Pressure (millitorr) DLI (ml/min) He Swp (sccm) O 2; (sccm) Working time (min) Refractive index n Thickness () Sedimentation rate (/mim) FTIR peak value (cm -1)
V1541 255 1000 0.1 100 100 5 1.954 784 156.8 1582.6
1.957 810 162.0 1583
2.177 891 178.2 2210
V1542 253 1000 0.1 100 100 5 1.959 737 147.4 1574
1.968 850 170.0 2210
1.972 918 183.6
Table V illustrates by sending Hf (N (CH simultaneously 2CH 3) 2) 4, SiH 2(CH 2CH 3) 2And O 2To the needed processing parameter of reactor cavity deposition Hf-Si-O film; " TDEAH and DES ".
Moreover as for the Zi-Si-O film, Table IV shows the refractive index ratio SiO of Hf-Si-O film 2The specific refractory power of film is much higher, like this specific inductivity k height of Hf-Si-O film.
Most important ground, the specific refractory power of Table V demonstration Hf-Si-O film changes with the relative concentration (representing with flow velocity) of the hafnium that uses in the CVD technology, silicon and oxygen.
For instance, Fig. 2 shows that the specific refractory power of Hf-Si-O film is as SiH 2(CH 2CH 3) 2The function of flow velocity (sccm), according to Table V.When other condition remained unchanged, this silicon precursor flow velocity changed between the 25sccm at 6.3sccm.Pressure is 1.5 holders; Chip temperature is 492 ℃; Metal (hafnium) precursor flow rate is 0.1ml/min; The helium carrier gas flow velocity is 100sccm; The HD gas flow rate is 0sccm; And oxygen gas flow rate is 100sccm.
Table V TDEAH and DES
Curve Chip temperature (℃) Pressure (m holder) DLI (ml/min) DES (sccm) O 2 (sccm) He dilutes (sccm) Depositing time (min) Sedimentation rate (/mim) Thickness () Refractive index n
1443-47-1 492 1.5 0.1 6.3 100 - 1.5 898 1347 1.9201
1443-47-2 492 1.5 0.1 6.3 100 - 1.5 1068 1602 1.9246
1443-48-1 492 1.5 0.1 10.3 100 - 1.5 1031 1546 1.8983
1443-48-2 492 1.5 0.1 14.3 100 - 1.5 999 1499 1.8459
1443-48-3 492 1.5 0.1 14.3 100 - 1.6 1093 1748 1.8451
1443-48-4 492 1.5 0.1 25 100 - 1.5 1477 2216 1.7599
1443-48-5 492 1.5 0.1 25 100 - 1 1417 1417 1.7870
1443-49-1 523 1.5 0.1 25 100 30 1 879 879 1.7881
1443-49-2 523 1.5 0.1 25 100 15 1 1366 1366 1.7558
1443-49-3 523 1.5 0.1 25 75 15 1 831 831 1.7095
1443-49-4 523 1.5 0.1 25 75 30 2.5 1408 3519 1.8332
1443-50-1 523 1.5 0.1 25 75 30 1 570 570 1.6874
1443-50-2 523 1.5 0.1 25 75 30 2.5 578 1444 1.7707
1443-50-3 523 1.5 0.1 25 75 0 1 164 164 1.3200
1443-50-4 511 1 0.1 25 100 0 1 1357 1357 1.8047
1443-50-5 493 0.5 0.1 25 100 0 1 1061 1061 1.8920
1443-50-6 493 0.5 0.1 25 100 5 1 1049 1049 1.9014
1443-51-1 493 0.5 0.05 25 100 5 1 792 792 2.0525
1443-51-2 511 1 0.1 45 100 15 1 1084 1084 1.7652
1443-51-3 511 1 0.1 45 100 10 1 1321 1321 1.7887
Outstanding feature shown in Fig. 2 is that the specific refractory power of Hf-Si-O film (specific inductivity of Hf-Si-O film like this) approximately linear ground reduces along with the increase of this silicon precursor flow velocity (the relative atom concentration that therefore causes silicon).Therefore, Fig. 2 clearly illustrates that the specific inductivity of hafnium silicate film can regulate based on the atomic percent of the hafnium in the film, silicon and oxygen.
Embodiment of the present invention listed above comprises that work embodiment is the example that constitutes many embodiments of the present invention.Should note to use many other settings in the technology, and the material that uses in the technology can be selected from other the numerous materials outside these concrete disclosed materials.In fact simple, the present invention is elaborated with reference to specific embodiment, but four corner of the present invention should be defined by the following claims.

Claims (16)

1. a formation comprises step as the method for the metal silicate of high-k dielectric in the electron device:
Provide diethylsilane to reaction zone;
Provide oxygen source to this reaction zone simultaneously;
Provide metal precursor to arrive this reaction zone simultaneously;
By chemical vapour deposition diethylsilane, oxygen source and metal precursor are reacted, to form metal silicate comprising on the substrate of this electron device.
2. the process of claim 1 wherein that described metal precursor selects from the group that is made of metal amide, metal alcoholate and composition thereof.
3. the method for claim 2, wherein said metal from by hafnium, zirconium, and composition thereof select the group that constitutes.
4. the process of claim 1 wherein that described oxygen source selects from the group that is made of oxygen, air, ozone and composition thereof.
5. the process of claim 1 wherein that diethylsilane, oxygen source and metal precursor react under the condition of chemical vapour deposition.
6. the method for claim 5, wherein said chemical vapor deposition conditions comprise the pressure of 0.5 to 2 holder and 250 ℃ to 450 ℃ temperature.
7. the method for claim 6, wherein said metal precursor flow velocity is 0.05 to 0.1 milliliter of per minute.
8. the method for claim 6, wherein purge gas is 100 to 150 standard cubic centimeter per minutes.
9. the method for claim 8, wherein said purge gas is selected from the group that is made of helium, argon, nitrogen and composition thereof.
10. the process of claim 1 wherein that the flow velocity with 5 to 100 standard cubic centimeter per minutes provides diethylsilane.
11. the process of claim 1 wherein that the residence time of diethylsilane, oxygen source and metal precursor is 0.05 to 2 second in the reaction.
12. the process of claim 1 wherein that the relative atom concentration by metal precursor, diethylsilane and oxygen in the change reaction zone changes the high k value of this metal silicate.
13. a formation comprises step as the method for the hafnium silicate of high-k dielectric in the electron device:
Provide diethylsilane to reaction zone;
Provide oxygen source to this reaction zone simultaneously;
Provide four (diethylin) hafnium to this reaction zone simultaneously;
By chemical vapour deposition this diethylsilane, oxygen source and four (diethylin) hafnium are reacted, to form hafnium silicate comprising on the substrate of this electron device.
14. the method for claim 13 wherein changes the high k value of this hafnium silicate by the relative atom concentration that changes four (diethylin) hafnium, diethylsilane and oxygen in the reaction zone.
15. a formation comprises step as the method for the zirconium silicate of high-k dielectric in the electron device:
Provide diethylsilane to reaction zone;
Provide oxygen source to this reaction zone simultaneously;
Provide four (diethylin) zirconium to this reaction zone simultaneously;
By chemical vapour deposition this diethylsilane, oxygen source and four (diethylin) zirconium are reacted, to form zirconium silicate comprising on the substrate of this electron device.
16. the method for claim 15 wherein changes the high k value of this zirconium silicate by the relative atom concentration that changes four (diethylin) zirconium, diethylsilane and oxygen in the reaction zone.
CNA2007101288016A 2006-05-30 2007-05-30 Diethylsilane as a silicon source in the deposition of metal silicate films Pending CN101125659A (en)

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US80925506P 2006-05-30 2006-05-30
US60/809255 2006-05-30
US11/747019 2007-05-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108822903A (en) * 2018-06-20 2018-11-16 湖南辰砾新材料有限公司 A kind of gasoline additive and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108822903A (en) * 2018-06-20 2018-11-16 湖南辰砾新材料有限公司 A kind of gasoline additive and preparation method thereof

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