CN104164660A - Low-dielectric-constant porous SiOCNH film and preparation method thereof - Google Patents

Low-dielectric-constant porous SiOCNH film and preparation method thereof Download PDF

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CN104164660A
CN104164660A CN201410425697.7A CN201410425697A CN104164660A CN 104164660 A CN104164660 A CN 104164660A CN 201410425697 A CN201410425697 A CN 201410425697A CN 104164660 A CN104164660 A CN 104164660A
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siocnh
mtes
limo
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CN104164660B (en
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丁士进
黄毅华
张卫
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Fudan University
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Abstract

The invention belongs to the technical field of manufacturing of very-large-scale integrated circuits, and particularly relates to a low-dielectric-constant porous SiOCNH film and a preparation method thereof. By using a PECVD (plasma enhanced chemical vapor deposition) technique, MTES and LIMO used as liquid sources are vaporized and carried into a cavity along with helium gas so as to be mixed with ammonia gas, the substrate temperature, radio-frequency power, working pressure in the reaction cavity, reaction source proportioning and other technological parameters in the deposition process are controlled to obtain an inorganic-organic composite film, and the inorganic-organic composite film is subjected to thermal annealing treatment to remove organic constituents, thereby finally obtaining the low-dielectric-constant porous SiOCNH film. The dielectric constant of the film is 2.38+/-0.06-2.58+/-0.05; the drain current density under the electric field intensity of 1 MV/cm is up to 10<-9>-10<-8>/cm<2> order of magnitude; the Young's modulus is 35.41-36.31GPa; and the hardness is 1.88-2.48GPa.Since the nitrogen element is doped into the film, the low-dielectric-constant porous SiOCNH film has favorable electric properties and excellent mechanical properties.

Description

A kind of low-k porous SiOCNH film and preparation method thereof
Technical field
The invention belongs to super large-scale integration manufacturing technology field, be specifically related to a kind of low-k porous SiOCNH film and preparation method thereof.
Background technology
Along with the develop rapidly of super large-scale integration, its characteristic dimension also reduces rapidly thereupon, and the caused resistance-capacitance of unicircuit post-channel interconnection (RC) delayed effect also becomes increasingly serious, is seriously restricting the lifting of chip performance.In order to reduce RC delayed effect, adopt low-k (k) material to replace traditional connected medium SiO 2(k ≈ 4.0) is the effective way [1] that improves chip performance.In order to obtain the dielectric material that k value is lower, except introduce Si-C key, Si-F key and the C-C key that polarity is less in medium [2,3], another kind of more effective method is in thin-film material, to introduce the hole of nanoscale.This is that the k value due to air is 1.Along with the increase of film mesoporosity rate, k value can reduce [4] quickly.Yet, low-k materials film containing vesicular structure wants to be applied to, in unicircuit, also must consider its thermostability, hydrophobicity, electric property etc. especially to have enough physical strengths, to meet the requirement [5,6] of CMP (Chemical Mechanical Polishing) process in unicircuit postchannel process.
At present, spin coating technique and plasma enhanced chemical vapor deposition (PECVD) technology is to prepare two kinds of main method of low-k materials film.PECVD technology because its growth temperature is low, sedimentation rate is fast and stress controllability is good etc., and advantage is widely used in industry member.In addition, utilize PECVD technology, in organic liquid source, mix pore former, and remove pore former by thermal anneal process, can obtain the low-k materials film of vesicular structure, but its mechanical property and electric property also face the risk of degeneration.Therefore the low-k materials and the preparation technology thereof that, find a kind of mechanical property excellence have important practical significance.
In order to improve the mechanical property of porous membrane in the situation that k value is lower, the present invention is with organic liquid source three-(ethoxymethyl) base silane (MTES), kautschin (LIMO) and ammonia (NH 3) be reaction raw materials, adopt PECVD technology and after annealing method to prepare low-k porous SiOCNH film.By introducing nitrogen element, in the situation that guaranteeing that porous membrane k value is lower, its mechanical property has also obtained effective improvement.
reference
[1]?International?Technology?Roadmap?for?Semiconductors?2011,?www.itrs.net.
[2]?S.?J.?Ding.?Chem.?Vap.?Deposition.?2001,?7,?4.
[3]?P.?F.?Wang.?et?al.?Appl.?Phys.?A.?2001,?72,?721.
[4]?T.?Jiang.?et?al.?J.?Mater.?Chem.?C.?2014,?2,?6502.
[5]?E.?P.?Guyer.?et?al.?J.?Mater.?Res.?2006,?21,?882.
[6]?A.?Grill.?et?al.?J.?Appl.?Phys.?2008,?103,?054104.
Summary of the invention
The object of the present invention is to provide a kind of low-k SiOCNH thin-film material with excellent mechanical property and good electrical performance and preparation method thereof.
The preparation method of porous low dielectric constant films material provided by the invention, adopts PECVD technology, with NH 3gas, kautschin (LIMO) and three-(ethoxymethyl) base silane (MTES) steam are reaction source, and deposition obtains inorganic-organic hybrid film, and process and obtain low k porous SiOCNH film through high-temperature thermal annealing; Concrete steps are as follows:
(1) at ambient temperature, wafer substrate is put on the pallet of plasma enhanced chemical vapor deposition (PECVD) equipment reaction cavity, then reaction chamber is vacuumized, make chamber vacuum degree reach 0.02 ~ 0.03 torr; Then, underlayer temperature is heated to 150 ~ 300 ℃;
(2), by the control of liquid under meter (LFM), the flow of three-(ethoxymethyl) base silane (MTES) and kautschin (LIMO) is set as respectively to 1 ~ 2 g/min, 1.5 ~ 3 g/min, and passes in vaporizer; MTES after vaporization, LIMO steam are loaded in reaction chamber along different gas circuits by He gas, and the carrier gas flux of wherein carrying MTES steam is 1000 ~ 6000 sccm, and carrying the carrier gas flux of LIMO steam is 2000 ~ 8000 sccm;
(3) another road reactant gases NH 3by mass flowmeter (MFC), controlled and directly entered in reaction cavity, its flow is 100 ~ 1000 sccm;
(4) NH 3, MTES and LIMO after He carrier gas, vaporization mix in reaction cavity, during pressure in question response cavity arrival set(ting)value 3 ~ 7 torr, stablizes 1 ~ 2 min, then open radio-frequency power supply, frequency is 13.56MHz, and radio frequency power is 100 ~ 800W, and deposition obtains inorganic-organic hybrid film;
(5) the inorganic-organic hybrid film obtaining is placed in to tube furnace, box-type furnace or other cavity and carries out thermal anneal process.Annealing temperature is 300 ~ 500 ℃, and annealing time is 1 ~ 5 hour, and annealing atmosphere can be argon gas, helium or nitrogen etc., and pressure is 0.1 ~ 800 torr.In annealing process, part organic constituent generation thermolysis, finally obtains low k porous SiOCNH film.
In the present invention, the thickness of described film is controlled by PECVD depositing time.The incorporation of pore former LIMO can regulate the k value size of film within the specific limits.
In the present invention, in described film, contain N-H, Si-O, Si-CH 3composition, referred to as SiOCNH film.This film has lower specific inductivity, and k value is 2.38 ± 0.06 ~ 2.58 ± 0.05; Under the strength of electric field of 1MV/cm, leakage current density is 10 -9~ 10 -8a/cm 2the order of magnitude; Young's modulus is 35.41 ~ 36.31 GPa, and hardness is 1.88 ~ 2.48 GPa, and mechanical property is outstanding.
Tool of the present invention has the following advantages:
(1) film provided by the invention has good homogeneity, and preparation process is simple, controllability is good, is applicable to large-scale mass production in industry;
(2) the low k thin-film material that prepared by the present invention has excellent mechanical property, and Young's modulus is 35.41 ~ 36.31 GPa, and hardness is 1.88 ~ 2.48 GPa, with respect to other low k thin-film materials, its aspect mechanical property in obvious leading position;
(3) the porous SiOCNH film that the present invention obtains also has good insulating property in mechanical property excellence, and under the strength of electric field of 1MV/cm, leakage current density is 10 -9~ 10 -8a/cm 2the order of magnitude.
Accompanying drawing explanation
Fig. 1 is Fourier transform infrared spectroscopy (FTIR) figure of the film that obtains of PECVD after thermal annealing.
Fig. 2 is cross section transmission electron microscopy mirror (TEM) photo after film thermal anneal.
Embodiment
1, wafer substrate is put into cavity at ambient temperature, reaction chamber is vacuumized simultaneously, make chamber vacuum degree reach 0.02 ~ 0.03 torr.Then underlayer temperature is risen to 150 ~ 300 ℃.In temperature, rise to after 150 ~ 300 ℃, to cavity, pass into He gas, gas piping is carried out to preheating, prevent that the liquid source of incomplete vaporization is condensate on tube wall.
2, by the control of LFM, the flow of three-(ethoxymethyl) base silane (MTES) and kautschin (LIMO) is set as respectively to 1 ~ 2g/min and 1.5 ~ 3g/min, and pass into vaporizer, MTES after vaporization and LIMO steam are loaded in reaction chamber along different gas circuits by He gas respectively, the He airshed of wherein carrying MTES steam is 1000 ~ 6000 sccm, and carrying the He airshed of LIMO steam is 2000 ~ 8000 sccm.
3, reactant gases NH 3by mass flowmeter (MFC), controlled and directly entered in reaction cavity, its flow is 100 ~ 1000 sccm.
4, in reaction cavity, NH 3, He carrier gas mixes with MTES and LIMO after vaporization, during pressure in question response cavity arrival set(ting)value 3 ~ 7 torr, then stablizes 1 ~ 2 min, then opens radio-frequency power supply (frequency is 13.56MHz), radio frequency power is 100 ~ 800W.After deposition 1 ~ 10 min, obtain inorganic-organic hybrid film.
5, this inorganic-organic hybrid film is placed in to tube furnace, box-type furnace or other cavity and carries out thermal anneal process, annealing temperature is 300 ~ 500 ℃, annealing time is 1 ~ 5 hour, and annealing atmosphere can be argon gas, helium, nitrogen etc., and pressure is 0.1 ~ 800 torr.In annealing process, part organic constituent generation thermolysis, finally obtains porous SiOCNH film.
In order to measure the electric property of above-mentioned porous SiOCNH film, the low resistance silicon chip (resistivity is 0.001-0.01 Ω cm) of take is substrate, according to above-mentioned technique, prepare porous SiOCNH film, utilize mask plate and electron beam evaporation technique,, diameter thick at SiOCNH film surface growth 300nm is the circular aluminum electrode of 400-420 μ m, for electrical testing., remove after silicon chip back side natural oxidizing layer growth one deck aluminium film, thereby the test structure of formation aluminium/SiOCNH film/silicon/aluminium meanwhile.In order further to improve the reliability of test structure, above-mentioned test structure is placed in to nitrogen hydrogen mixeding gas (N 2/ H 2) middle annealing 1 hour, annealing temperature is 200 ℃.Then, by the measurement of the capacitance-voltage characteristics of this structure is extracted to specific inductivity, and obtain reliably average k value by multimetering.In addition, by the measurement to the I-E characteristic of this structure, obtain leakage current density.The mechanical property of film and Chemical Composition record by nano-hardness tester and Fourier transform infrared spectroscopy (FTIR) respectively.
Accompanying drawing 1 is the FTIR figure after inorganic-organic hybrid Thin-film anneal.800cm -1and 1050cm -1near the peak position that absorbs is corresponding to the Si-O structure of film, 1590cm -1near absorption peak is corresponding to N-H structure, and this shows NH 3n element in gas has successfully been incorporated in silicon oxide film, N element be mixed with the mechanical property that helps improve material.1270cm -1near absorption peak derives from Si-CH 3stretching vibration, show to contain in this film a certain amount of CH 3group, it be mixed with the k value that helps reduce film.2890cm -1peak is corresponding to the CH in film xstructure, though pore former has certain remnants, CH after annealing xpeak area is compared much smaller with Si-O peak area.Accompanying drawing 2 is transmission electron microscope (TEM) photo of SiOCNH film, can clearly see and in this film, contain a large amount of nanoaperture, this shows that pore former is removed in a large number after thermal anneal process, thereby forms vesicular structure, this major cause that film k value reduces just.
Subordinate list 1 has been listed MTES and NH 3electricity and the mechanical experimental results of under throughput ratio different situations, preparing gained film.From this table, thin-film dielectric constant is 2.38 ± 0.06 ~ 2.58 ± 0.05.Under 1MV/cm strength of electric field, leakage current density is all in 10 -9~ 10 -8a/cm 2the order of magnitude, has shown extraordinary insulating property.From this table, the Young's modulus of two kinds of films is 35.41 ~ 36.31 GPa, and hardness is 1.88 ~ 2.48 GPa, all shows very excellent mechanical property.
Subordinate list 1 Electrical and mechanical experimental results SHAPE * MERGEFORMAT
?。

Claims (2)

1. a preparation method for low-k porous SiOCNH film, is characterized in that: adopt PECVD technology, with NH 3gas, LIMO and MTES steam are reaction source, and deposition obtains inorganic-organic hybrid film, then process and obtain low-k porous SiOCNH film through high-temperature thermal annealing; Concrete steps are as follows:
(1) at ambient temperature, wafer substrate is put on the pallet of PECVD equipment reaction cavity, then reaction chamber is vacuumized, make chamber vacuum degree reach 0.02 ~ 0.03 torr; Then, underlayer temperature is heated to 150～300 ℃;
(2), by the control of liquid under meter, with the flow of 1～2 g/min, 1.5～3 g/min, MTES and LIMO are passed in vaporizer respectively; MTES after vaporization, LIMO steam are loaded in reaction chamber along different gas circuits by He gas, and the carrier gas flux of wherein carrying MTES steam is 1000 ~ 6000 sccm, and carrying the carrier gas flux of LIMO steam is 2000 ~ 8000 sccm; Here, LIMO is kautschin, and MTES is three-(ethoxymethyl) base silane;
(3) another road reactant gases NH 3by mass flowmeter, controlled and directly entered in reaction cavity, its flow is 100～1000 sccm;
(4) NH 3, He carrier gas, vaporization after MTES and LIMO in reaction cavity, mix, when the pressure in question response cavity arrives set(ting)value 3～7 torr, stablize 1～2 min, then open radio-frequency power supply, frequency is 13.56MHz, radio frequency power is 100～800W, and deposition obtains inorganic-organic hybrid film;
(5) the inorganic-organic hybrid film obtaining is placed in to tube furnace, box-type furnace or other cavity and carries out thermal anneal process; Annealing temperature is 300～500 ℃, and annealing time is 1 ~ 5 hour, and annealing atmosphere is argon gas, helium or nitrogen, and pressure is 0.1 ~ 800 torr, finally obtains low-k porous SiOCNH film.
2. by preparation method described in claim 1, prepare a low-k porous SiOCNH film, in described film, contain N-H, Si-O, Si-CH 3composition; Its specific inductivity k value is 2.38 ± 0.06～2.58 ± 0.05; Under the strength of electric field of 1MV/cm, leakage current density is 10 -9～10 -8a/cm 2the order of magnitude; Young's modulus is 35.41～36.31 GPa, and hardness is 1.88～2.48 GPa.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105762109A (en) * 2014-12-19 2016-07-13 中芯国际集成电路制造(上海)有限公司 Formation method of semiconductor structure

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030087043A1 (en) * 2001-11-08 2003-05-08 International Business Machines Corporation Low k dielectric film deposition process
JP2005019980A (en) * 2003-05-29 2005-01-20 Air Products & Chemicals Inc Method of fabricating low-dielectric-constant organic silicate glass film
US20070155186A1 (en) * 2005-11-22 2007-07-05 International Business Machines Corporation OPTIMIZED SiCN CAPPING LAYER
CN101187011A (en) * 2006-11-21 2008-05-28 应用材料股份有限公司 Method of improving initiation layer for low-k dielectric film by digital liquid flow meter
JP2008519980A (en) * 2004-11-12 2008-06-12 トヨタ モーター マニュファクチュアリング、ノース アメリカ インク System and method for inspecting coatings, surfaces and interfaces
JP2008306182A (en) * 2007-06-06 2008-12-18 Asm Japan Kk Method for forming inorganic silazane base insulation film
WO2014070619A1 (en) * 2012-11-01 2014-05-08 Applied Materials, Inc. Method of patterning a low-k dielectric film
CN103956331A (en) * 2014-04-29 2014-07-30 复旦大学 Thin film used for hole sealing of porous interconnection dielectric surface and preparing method of thin film

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030087043A1 (en) * 2001-11-08 2003-05-08 International Business Machines Corporation Low k dielectric film deposition process
JP2005019980A (en) * 2003-05-29 2005-01-20 Air Products & Chemicals Inc Method of fabricating low-dielectric-constant organic silicate glass film
JP2008519980A (en) * 2004-11-12 2008-06-12 トヨタ モーター マニュファクチュアリング、ノース アメリカ インク System and method for inspecting coatings, surfaces and interfaces
US20070155186A1 (en) * 2005-11-22 2007-07-05 International Business Machines Corporation OPTIMIZED SiCN CAPPING LAYER
CN101187011A (en) * 2006-11-21 2008-05-28 应用材料股份有限公司 Method of improving initiation layer for low-k dielectric film by digital liquid flow meter
JP2008306182A (en) * 2007-06-06 2008-12-18 Asm Japan Kk Method for forming inorganic silazane base insulation film
WO2014070619A1 (en) * 2012-11-01 2014-05-08 Applied Materials, Inc. Method of patterning a low-k dielectric film
CN103956331A (en) * 2014-04-29 2014-07-30 复旦大学 Thin film used for hole sealing of porous interconnection dielectric surface and preparing method of thin film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YOSHIMI SHIOYA，ET AL.: ""Properties of Low-k Cu Barrier SiOCNH Film Deposited by Plasma-Enhanced Chemical Vapor Deposition using Hexamethyldisiloxane and Ammonia Gases"", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105762109A (en) * 2014-12-19 2016-07-13 中芯国际集成电路制造(上海)有限公司 Formation method of semiconductor structure
CN105762109B (en) * 2014-12-19 2019-01-25 中芯国际集成电路制造(上海)有限公司 The forming method of semiconductor structure

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