CN102618828A - Hf-based high-k gate dielectric film and production method thereof - Google Patents

Hf-based high-k gate dielectric film and production method thereof Download PDF

Info

Publication number
CN102618828A
CN102618828A CN2012100798262A CN201210079826A CN102618828A CN 102618828 A CN102618828 A CN 102618828A CN 2012100798262 A CN2012100798262 A CN 2012100798262A CN 201210079826 A CN201210079826 A CN 201210079826A CN 102618828 A CN102618828 A CN 102618828A
Authority
CN
China
Prior art keywords
gate dielectric
dielectric film
source
ion beam
ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2012100798262A
Other languages
Chinese (zh)
Inventor
余涛
金成刚
吴雪梅
诸葛兰剑
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN2012100798262A priority Critical patent/CN102618828A/en
Publication of CN102618828A publication Critical patent/CN102618828A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Insulated Gate Type Field-Effect Transistor (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

The invention discloses a production method of an Hf-based high-k gate dielectric film, which includes the steps: (a), using a dual ion beam sputtering-deposition system to adjust background vacuum into 2X10-4-5X10-4Pa, and adjust working air pressure into 3.0X10-2-3.2X10-2Pa; (b), dryly cleaning with an auxiliary source; (c), passivating the surface of a substrate with the auxiliary source; and (d), depositing a film to obtain the Hf-based high-k gate dielectric film. The surface of the Hf-based high-k gate dielectric film produced by the method is quite uniform and even, surface RMS (root mean square) roughness is 0.16 nanometer only, crystallization temperature reaches 1100 DEG C, C-V saturation characteristic is excellent, C-V hysteresis is nearly neglected, and accordingly solid material and technical basis is laid for finally producing high-k material systems meeting CMOS (complementary metal-oxide-semiconductor) application with technical nodes smaller than 45-32nm.

Description

Compound high-k gate dielectric film of a kind of Hf base and preparation method thereof
Technical field
The present invention relates to compound high-k gate dielectric film of a kind of Hf base and preparation method thereof, belong to field of semiconductor materials.
Background technology
After nineteen sixty MOSFET device was succeeded in developing, to become core indispensable in the advanced unicircuit such as microprocessor and semiconductor memory flourish rapidly because of it has advantages such as reduce power consumption, safety are high, size is easy to dwindle.In order to increase the function of device density, response speed and chip, the scaled of device size is CMOS technology development trend for a long time.Yet traditional grating oxygen material SiO 2Arrived its physics limit thickness.For solving this difficult problem, select for use high k (specific inductivity) gate dielectric material to substitute SiO 2Become the inexorable trend of microelectronics development.
Yet, be not that all high k materials all possess the condition that becomes gate dielectric material.Through the big quantity research and the effort of domestic and international researchist's many decades, high k material has been proposed some basic demand: (1) has high Tc; Because non-crystalline state is the optimal structure of gate dielectric layer, except experimentally being easy to preparation, more chief reason is the isotropic advantage of crystal grain in the non-crystalline state, has avoided the existence of grain boundary in the grid oxide layer; (2) high-k; High k value can be kept enough drive currents, and can keep same equivalent thickness (E OT) prerequisite under, increase the actual physics thickness of grid oxide layer, the sub-tunneling effect of effective inhibitory amount greatly; (3) keep good thermodynamic stability with the Si substrate, and and the Si conduction band between deviation greater than 1eV; (4) have big energy gap, high potential barrier; (5) low gate oxide electric density and boundary defect.
In recent years, the various countries researchist is to Hf base high-K gate dielectric material (HfO especially 2) given great concern.Why so these materials striking its considerable dielectric constant values (k=20～25) that is, wide band gap is bigger with the conduction band offset amount of Si, and excellent thermostability.Although HfO 2Gather plurality of advantages, but have three big intrinsic difficult problems.One of which, HfO 2Tc very low (400 ℃), anneal will cause phase transformation, cause the degeneration of electrical properties.Its two, be prone to reaction with the Si substrate and form the hafnium silicide, cause EOT to increase.Its three, the mobility of charge carrier rate is on the low side in the Hf base grid medium MOS FET device, some even not enough SiO 2Half the.
At present, the method for preparing high-k gate dielectric material has multiple: pulse laser, magnetron sputtering, molecular beam epitaxy, chemical vapour deposition, ald, electron beam evaporation and sol-gel etc.These deposition process differ from one another, and cut both ways.Also there are some drawbacks in the atomic deposition technique of wherein being accepted by people, and for example: worsen at the interface, and growth cycle is longer, problems such as presoma residual impurity pollution.
In long-term following period of time from now on, people will be growing on and on to the research temperature of high-k gate dielectric material, and this is the inexorable trend that advanced CMOS technology develops rapidly.How significantly improving carrier mobility, effectively suppress diffusion of contaminants, obtain excellent interfacial characteristics, optimize the electricity safety, further improve and develop preparation technology, will be the focal issue in the high k composite grid dielectric material research.
Summary of the invention
The object of the invention provides compound high-k gate dielectric film of a kind of Hf base and preparation method thereof.
For achieving the above object, the technical scheme that the present invention adopts is: the preparation method of the compound high-k gate dielectric film of a kind of Hf base comprises the steps:
(a) adopt double ion beam sputtered depositing system, with its base vacuum furnishing 3 * 10 -4~ 5 * 10 -4Pa, operating air pressure furnishing 3.0 * 10 -2~ 3.2 * 10 -2Pa;
(b) auxilliary source dry method cleaning: the source of will assisting feeds Ar gas, is cleaning early stage, and the employing ion energy is 200 ~ 300eV, and ion beam current 15 ~ 20mA carries out the icon bombardment cleaning substrate, and the time is 1 ~ 2min; Then ion energy is adjusted to 80 ~ 100eV, ion beam current is adjusted to 8 ~ 10mA, proceeds ion bombardment, further the polished substrate surface;
(c) Passivation Treatment is carried out to substrate surface in auxilliary source: will assist the mixed gas that the source feeds Ar and N, Ar:N 2Be 2 ~ 3:1; Adopt ion energy 100 ~ 150eV, ion beam current 8 ~ 10mA, sputter substrate surface 1 ~ 3min;
(d) deposit film: main source is with ion energy 700 ~ 800eV, ion beam current 45 ~ 50mA sputtering target material, and auxilliary source 30s before thin film deposition be a closing condition in the time, opens the source of assisting behind the 30s, and with ion energy 150 ~ 200eV, ion beam current 12 ~ 15mA sputter substrate; Can obtain the compound high-k gate dielectric film of Hf base.
In the preceding text, during step (b) dry method is cleaned, adopt early stage bigger ion energy can improve etching surface SiO 2Speed, the later stage is reduced ion energy, is for the smooth substrate surface, for growth for Thin Film provides the fine physical support.
The Passivation Treatment of step (c), experimental result show the effectively dangling bonds at passivation interface place of N, generate layer of sin as thin as a wafer x(k ~ 4-5), further reduce interface state density optimizes interfacial characteristics to layer.Also can select the O plasma treatment here, artificial introducing one deck high-density SiO as thin as a wafer 2, form stacking provisions thus.
In the process of the deposit film of step (d); Auxilliary source emission reactant gases bombards sedimentary atom; Then ion and deposition and atomic generation chemical reaction at the substrate surface synthetic compound, and are accomplished the chemical ingredients proportioning of controlling film, the ion beam modification that changes film microstructure and character etc.
The deposition table of double ion beam sputtered depositing system has water quench to handle, and in thin film growth process, remains the normal temperature state.
In the technique scheme, in said step (d) before, earlier, remove its surface contaminant with composite target material sputter 5min at least.
In the technique scheme, the depositing time 3 ~ 5min of said step (d).
The present invention asks for protection the compound high-k gate dielectric film of Hf base that is obtained by above-mentioned preparation method simultaneously.
Ultimate principle of the present invention is: the ion of bombardment material target surface causes the cascade collision of target upper layer atom when shifting self-contained energy or momentum, makes the part target atom break away from the target surface and forms sputtered atom; If in the sputtered atom flux, substrate is set; The sputtered atom that then carries certain energy is deposited on substrate surface; Along with continuing of sputter deposition process; Deposition and atomic, forms and growing film with modes such as island mode, laminated form or unordered atom packings through nucleation and grain growing at substrate surface; Auxilliary therebetween source is launched different types of gas plasma bundle and is used to remove substrate surface adsorptive, pollutent and oxide compound on the one hand.On the other hand, auxilliary source ion bombardment has changed surface tissue, improved deposition and atomic the activated point bit density, increase the surface mobility of deposition and atomic and greatly improved deposition and atomic and substrate surface atomic interaction state, be used for enhancement film and grow.Therefore, auxilliary source ion Shu Qingxi given the DIBSD film have high-adhesion and with the strong matching capacity of substrate material.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. the present invention has developed the preparation method of the compound high-k gate dielectric film of a kind of new Hf base; Prepared the compound high k film of high-quality Hf base with its stacking provisions, experiment shows that very homogeneous is smooth on the surface of the high-k gate dielectric film that employing the present invention makes; Surface r.m.s. roughness RMS only has 0.16nm; Tc has excellent C-V saturation characteristic, almost insignificant C-V hysteretic phenomenon up to 1100 ℃; Thereby, establish solid material and technical foundation for finally preparing the high k material system that satisfies the following technology node CMOS application of 45 ~ 32nm.
2. preparation method of the present invention adopts existing double ion beam sputtered depositing system, and operation is simple, has active operation significance.
Description of drawings
Fig. 1 is the preparation flow figure of the embodiment of the invention one;
Fig. 2 is not anneal Hf in the embodiment of the invention one 1-xTa xO 1-yN yThe AFM figure of sample;
Fig. 3 is Hf in the embodiment of the invention one 1-xTa xO 1-yN yXRD figure spectrum;
Fig. 4 is Pt/HfTaON/SiN in the embodiment of the invention one xThe C-V characteristic curve of/Si electric capacity;
Fig. 5 is Pt/HfTaON/SiN in the embodiment of the invention one xThe I-V characteristic curve of/Si electric capacity.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one
The preparation method of the compound high-k gate dielectric film of a kind of Hf base is with HfM xO yN/SiN xStacking provisions is an example, adopts double ion beam sputtered deposition technique on traditional silicon (Si) and novel (SiGe, SOI) substrate, to prepare ultra-thin HfM xO yN/SiN x
Through regulating main source and auxilliary source ion beam energy, line size and feeding Ar/N gas ratio and Passivation Treatment (the formation SiN of auxilliary source in the auxilliary source to removing natural oxidizing layer Si substrate x), prepared the compound high k film of high-quality Hf base with its stacking provisions (comprise and improve thin film crystallization temperature, compactness, interfacial characteristics and specific inductivity), specifically parameter and technical process (with reference to figure 1) are as follows:
1) base vacuum 5 * 10 -4Pa; Operating air pressure 3.2 * 10 -2Pa;
2) assist source dry method cleaning parameters: the source of will assisting feeds Ar gas, is cleaning early stage, adopts ion energy (300eV), ion beam current (20mA) etching 2min; Change ion energy into 100eV in the later stage, ion beam current changes 10mA into, continues 3min; Adopt early stage bigger ion energy can improve etching surface SiO 2Speed, the later stage changes 100eV into, is for smooth substrate surface, for growth for Thin Film provides the fine physical support;
3) auxilliary source is to the substrate surface Passivation Treatment: will assist the mixed gas that the source feeds Ar and N, Ar:N 2Ratio is made as 2:1; With ion energy 100eV, the condition sputter substrate surface 2min of ion beam current 10mA; Experimental result shows the effectively dangling bonds at passivation interface place of N, generates layer of sin as thin as a wafer x(k ~ 4-5), further reduce interface state density optimizes interfacial characteristics to layer;
4) deposition film parameter: before the deposit film, earlier with composite target material sputter 5min to remove surface contaminant; When waiting to begin to deposit, main source is with ion energy 800eV, the processing parameter sputtering target material of ion beam current 50mA; Auxilliary source 30s before thin film deposition be closing condition in the time, and this is the Si atom to be activated when preventing auxilliary source sputter substrate, thereby is introducing the low k layer of hafnium silicate at the interface, in addition in film introduction Si element; Behind the 30s, open in the source of will assisting, and with ion energy 200eV, ion beam current 15mA sputter substrate can successfully be mixed into film with N on the one hand, makes film growth mode type of trending towards stratiform on the other hand, increases the degree of disorder;
5) deposition table has water quench to handle, and in thin film growth process, remains the normal temperature state, depositing time 4min.
Obtained Hf according to above preparation method 1-xTa xO 1-yN y/ SiN x/ Si; Experimental result shows: 1) firm sedimentary Hf 1-xTa xO 1-yN yUnder the situation of not doing any anneal, surface very homogeneous is smooth, and surperficial r.m.s. roughness RMS only has 0.16nm (like Fig. 2); 2) Tc is up to 1100 ℃ (like Fig. 3); 3) the C-V saturation characteristic of excellence, almost insignificant C-V hysteretic phenomenon explains that the film of passivation possesses excellent interfacial characteristics and less zone of oxidation electric density (like Fig. 4); 4) has less leakage current (at V g=+1V, I ~ 10 -10A), as shown in Figure 5; Compared with not passing through N 2The Hf that handles 1-xTa xO 1-yN yFilm, electric leakage will be low to moderate an one magnitude.
Method of the present invention possesses when the high k material of deposit can't substituted advantage: (one) can carry out the icon bombardment cleaning substrate at high vacuum condition, to remove surperficial organic pollutant and natural oxidizing layer (SiO 2), this dry method cleaning performance of producing with the physical sputtering form is can not be substituted with acidity or basic soln wet-cleaned institute.When enough hour of auxilliary source ion beam energy, further polished substrate surface also was for growth for Thin Film provides the fine physical support.(2) after dry method is cleaned completion, continue N plasma bombardment substrate surface with less energy, carry out Passivation Treatment.N is passivation Si substrate surface dangling bonds effectively, thereby reduce interface state density.Also can select the O plasma treatment, artificial introducing one deck high-density SiO as thin as a wafer 2, form stacking provisions thus, because Si/SiO 2Lattice match good, also can reach the effect that reduces interface state density, but can sacrifice total dielectric constant.(3) in the process of deposit film; Auxilliary source emission reactant gases bombards sedimentary atom; Then ion and deposition and atomic generation chemical reaction at the substrate surface synthetic compound, and are accomplished the chemical ingredients proportioning of controlling film, the ion beam modification that changes film microstructure and character etc.Specifically come, can make the film growth mode by island type of becoming stratiform through the energy in tuning auxilliary source ion source.Island in most cases is microlitic structure, often is attached to substrate surface with particular crystal plane, and this is to cause the lower main arch-criminal of high k thin film crystallization temperature.Secondly, can not merge between island and the island, leave narrow " empty road ", when the island structure continued growth, " empty road " is deposited atom and fills gradually, but often can not tamp and leave the space, is difficult to prepare ultrathin film.Fortunately, the reverse sputtering effect in auxilliary source makes early growth period cave in, tamp at " island " shape nucleus of substrate surface cohesion, thereby forms high crystallization temperature and fine and close ultra-thin high k film.Reduce the film grain size simultaneously, thus the fine and close more gate dielectric membrane of preparation; The auxilliary source ion bundle of less energy can effectively reduce the roughness of deposit film, thereby suppresses long-range scattering effect; Growth phase can increase the unordered degree of film, significantly improves the thin film crystallization temperature; Also but activation substrate surface atom is active, increases adhesive force.

Claims (4)

1. the preparation method of the compound high-k gate dielectric film of Hf base is characterized in that, comprises the steps:
(a) adopt double ion beam sputtered depositing system, with its base vacuum furnishing 3 * 10 -4~ 5 * 10 -4Pa, operating air pressure furnishing 3.0 * 10 -2~ 3.2 * 10 -2Pa;
(b) auxilliary source dry method cleaning: the source of will assisting feeds Ar gas, is cleaning early stage, and the employing ion energy is 200 ~ 300eV, and ion beam current 15 ~ 20mA carries out the icon bombardment cleaning substrate, and the time is 1 ~ 2min; Then ion energy is adjusted to 80 ~ 100eV, ion beam current is adjusted to 8 ~ 10mA, proceeds ion bombardment, further the polished substrate surface;
(c) Passivation Treatment is carried out to substrate surface in auxilliary source: will assist the mixed gas that the source feeds Ar and N, Ar:N 2Be 2 ~ 3:1; Adopt ion energy 100 ~ 150eV, ion beam current 8 ~ 10mA, sputter substrate surface 1 ~ 3min;
(d) deposit film: main source is with ion energy 700 ~ 800eV, ion beam current 45 ~ 50mA sputtering target material, and auxilliary source 30s before thin film deposition be a closing condition in the time, opens the source of assisting behind the 30s, and with ion energy 150 ~ 200eV, ion beam current 12 ~ 15mA sputter substrate; Can obtain the compound high-k gate dielectric film of Hf base.
2. the preparation method of the compound high-k gate dielectric film of Hf according to claim 1 base is characterized in that: in said step (d) before, with composite target material sputter 5min at least, remove its surface contaminant earlier.
3. the preparation method of the compound high-k gate dielectric film of Hf base according to claim 1 is characterized in that: the depositing time 3 ~ 5min of said step (d).
4. the compound high-k gate dielectric film of Hf base that preparation method according to claim 1 obtains.
CN2012100798262A 2012-03-23 2012-03-23 Hf-based high-k gate dielectric film and production method thereof Pending CN102618828A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2012100798262A CN102618828A (en) 2012-03-23 2012-03-23 Hf-based high-k gate dielectric film and production method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2012100798262A CN102618828A (en) 2012-03-23 2012-03-23 Hf-based high-k gate dielectric film and production method thereof

Publications (1)

Publication Number Publication Date
CN102618828A true CN102618828A (en) 2012-08-01

Family

ID=46559024

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012100798262A Pending CN102618828A (en) 2012-03-23 2012-03-23 Hf-based high-k gate dielectric film and production method thereof

Country Status (1)

Country Link
CN (1) CN102618828A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107910255A (en) * 2017-11-03 2018-04-13 武汉新芯集成电路制造有限公司 A kind of method for improving the dangling bonds bonding of wafer interface
CN109638111A (en) * 2018-12-19 2019-04-16 中国电子科技集团公司第十研究所 A kind of method of infrared detector surface treatment

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
TAO YU ET AL.: "The structure and electrical properties of HfTaON high-k films prepared by DIBSD", 《APPLIED SURFACE SCIENCE》 *
X.M.YANG等: "The influence of assisted ion beam bombardment on structure and electrical characteristics of HfSiO dielectric synthesized by DIBSD", 《MICROELECTRONICS RELIABILITY》 *
洪波: "工作参数对SiCN薄膜制备和性质的影响", 《中国优秀硕士学位论文全文数据库（电子期刊）》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107910255A (en) * 2017-11-03 2018-04-13 武汉新芯集成电路制造有限公司 A kind of method for improving the dangling bonds bonding of wafer interface
CN109638111A (en) * 2018-12-19 2019-04-16 中国电子科技集团公司第十研究所 A kind of method of infrared detector surface treatment

Similar Documents

Publication Publication Date Title
CN101800196B (en) Adjustment method of bimetal gate work function
KR101126650B1 (en) Method of Manufacturing Dielectric Film
CN103545211A (en) Production method of semiconductor device
TW200910532A (en) Non-volatile memory device and method for manufacturing the same
CN102453866A (en) High-dielectric-constant gate dielectric material and preparation method thereof
CN102629559A (en) Manufacture method of stacked gate SiC-metal insulator semiconductor (MIS) capacitor
CN102618828A (en) Hf-based high-k gate dielectric film and production method thereof
CN101728257A (en) Preparation method of gate dielectric/ metal gate integrated structure
KR20170093428A (en) HYDROGEN TREATED NbO2 THIN FILM, METHOD OF FABRICATING THE NbO2 THIN FILM AND ELECTROIC ELEMENT COMPRISING THE NbO2 THIN FILM
CN102810541B (en) A kind of memory and manufacture method thereof
CN102168268A (en) Preparation method of metal nanocrystal
CN106319460B (en) A kind of PVD process of metallic film sputtering
CN111430228A (en) Preparation method of dielectric film with ultrahigh dielectric constant
CN102760657A (en) Method for preparing high K grating medium film and MIS (Management Information System) capacitor on InP (Indium Phosphide) substrate
CN101831618B (en) Gate dielectric film with TiO2/ZrO2 two-layer stack structure and high dielectric constant and preparation method thereof
CN108172613A (en) A kind of zirconium base gate dielectric material with high-k crystalline phase with and preparation method thereof
CN102509732B (en) Low-power-consumption embedded phase-change memory used in microcontroller, phase-change storing material thereof, and preparation method thereof
CN102779845A (en) Laminated metallic oxide gate dielectric layer and preparation method thereof
CN103811304A (en) GeSn layer and forming method thereof
CN103839775A (en) GeSn layer of selected area and method for forming GeSn layer of selected area
CN103972105A (en) MOSFET with SiGe channel and forming method of MOSFET
CN103839980B (en) MOSFET with SiGeSn source drain and forming method thereof
CN103545202B (en) Pmos transistor and forming method thereof
CN107369760A (en) A kind of phase-change thin film for phase transition storage and preparation method thereof
CN102623311A (en) Apparatus for preparing metal nitride barrier layer and application method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20120801