CN208848856U - A kind of dielectric film of people's structure high dielectric constant - Google Patents
A kind of dielectric film of people's structure high dielectric constant Download PDFInfo
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Abstract
The utility model provides a kind of dielectric film of people's structure high dielectric constant.The dielectric film includes multiple sub- film units being periodically overlapped, and each unit is overlapped by the sub- film of low drain electric material and the sub- film of high dielectric material, and the thickness of each straton film is respectively less than 1nm；The bottom of dielectric film and top layer are the sub- film of low drain electric material；The sub- film of low drain electric material and high dielectric material can use one or more different materials；When dielectric film uses a variety of different materials, in every sub- film unit, each sub- film is first incremented by the sequence successively decreased again by leakage current by the bottom and arranged, or the sequence arrangement for first successively decreasing again incremental by forbidden bandwidth.People's structure high K dielectric film of the utility model has high dielectric constant and low-leakage current, can be prepared at low temperature.
Description
Technical field
The utility model relates to electronic technology field more particularly to a kind of people's structure high K dielectric membrane structures.
Background technique
High K dielectric film is because substantially single in super large-scale integration such as transistor, memory, thin-film capacitors
Extensive use in first electronic device and given more sustained attention, these requirement on devices dielectric films will not only possess high dielectric constant
And there must be low leakage current.Huge micro- integrated electronic or photonics on the glass or flexible substrate that newly-developed gets up are more
It is required that high K dielectric film must deposit at low temperature.
Reported research (Davide Ceresoli and David Vanderbilt, Structural and
dielectric properties of amorphous ZrO2and HfO2,Phys.Rev.B 74,125108–
Published 13September 2006) or patent (such as CN102208442A), it is concentrated mainly on hafnium silicate, zirconium silicate, two
The laminated film that hafnium oxide, zirconium dioxide or they and other materials are built up, but use these films as MIM veneer plane capacitor
In medium, capacitance density is difficult more than 20fF/um2, and the physical thickness of film is all several or more than ten nanometers, this makes
Film is easy to by machinery breakdown and electrical breakdown, to influence the reliability of device.
Summary of the invention
For deficiency existing for the above existing dielectric film, the utility model provides one kind and is able to satisfy large-scale integrated electricity
Road, huge microelectronics or optoelectronic intagration system required high dielectric constant, can be prepared, reliability low-leakage current at low temperature
Good high K dielectric film.
The purpose of this utility model is achieved through the following technical solutions:
A kind of dielectric film of people's structure high dielectric constant, the dielectric film include multiple sub- film lists being periodically overlapped
Member, every sub- film unit are overlapped by the sub- film of low drain electric material and the sub- film of high dielectric material, and each straton is thin
The thickness of film is respectively less than 1nm；The bottom of the dielectric film and top layer are the sub- film of low drain electric material；The low drain
The sub- film of electric material is using one or more kinds of different materials；The sub- film of the high dielectric material is using one or more kinds of
Different materials；When the dielectric film uses a variety of different materials, in every sub- film unit, each sub- film is pressed by the bottom
Leakage current is first incremented by the sequence arrangement successively decreased again, or the sequence arrangement for first successively decreasing again incremental by forbidden bandwidth.
Further, in every sub- film unit, the sub- film of the bottom is the smallest sub- film of dielectric constant.
Further, the sub- film of the low drain electric material uses intrinsic or doping hafnium oxide, hafnium silicate, oxidation
One in zirconium, zirconium silicate, gadolinium acid lanthanum, silica, silicon nitride, silicon oxynitride, tantalum oxide or alloy based on them, mixed crystal
Kind is a variety of.
Further, the sub- film of the high dielectric material using intrinsic or doping titanium oxide, SrTiOx, ZnOx or
One or more of alloy, mixed crystal based on them.
Further, surface and lower surface are equipped with one layer on it for the lower surface, upper surface of the dielectric film or difference
The electric leakage flow barrier of several nanometer thickness.
Further, the electric leakage flow barrier uses inorganic oxide material or organic self assembled monolayer material.
Preferably, the inorganic oxide material be intrinsic or doping hafnium oxide, hafnium silicate, zirconium oxide, zirconium silicate,
One of gadolinium acid lanthanum, silica, silicon nitride, silicon oxynitride, tantalum oxide or alloy based on them, mixed crystal are more
Kind.
Preferably, organic self assembled monolayer material uses the positive octadecyl ester of phosphoric acid, 1- tetradecyl phosphoric acid, 1- decyl
The self assembled monolayer that phosphoric acid or 1- butyl phosphoric acid are formed.
Compared with prior art, the beneficial effects of the utility model are as follows:
(1) the utility model is alternately stacked using the periodicity of the different sub- thin-film material of forbidden bandwidth, dielectric constant, shape
At a kind of people's structure high K dielectric film with high dielectric constant, low-leakage current.
(2) people's structure dielectric film of the utility model utilizes the low drain electric thin of sub-nanometer thickness, the height of sub-nanometer thickness
The physical effect of the periodic stack of the sub- film of dielectric constant obtains high dielectric constant, using this technology can prepare and dioxy
SiClx uniform thickness effective dielectric constant is more than 200 high dielectric thin film.
(3) people's structure dielectric film of the utility model makees the dielectric layer of veneer MIM capacitor, under 1V bias voltage,
Capacitance density is up to 30fF/ μm2, hence it is evident that higher than the capacitance density for the similar veneer thin-film capacitor announced.
(4) physical thickness of the dielectric film of the utility model is at 20 nanometers or more, than conventional SiO2, HfO2, Al2O3,
SiNx thickness much so that the electrical and mechanical performance of corresponding MIM device has better reliability and stability；It is practical new with this
The veneer MIM capacitor of people's structure high dielectric thin film preparation of type is compared with the comparable homogeneous mono-layers thin-film capacitor of capacitor, breakdown
It is more that voltage improves 3V；TDDB (Time-Dependent Dielectric Breakdown, electric field stress puncture the service life) shows
Under identical electric field bias, the people of the utility model is significantly improved in the structure high dielectric thin film MIM capacitor service life, TDDB prediction of result
10 year service life electric field stress improve 8MV/cm or more.
(5) people's structure high K dielectric film of the utility model, can with but be not limited to atomic layer deposition
(ALD), chemical vapor deposition method lower than 300 degrees Celsius at a temperature of be prepared, meet the needs of low temperature preparation.
(6) dielectric film of the utility model can be used as the medium of capacitor, the insulating layer of field effect transistor, memory
The medium etc. of part may be not only suitable in electronic device, circuit or the system on traditional high temperature-resistant liner such as crystalline silicon, quartz bottom,
It can be applicable in the electronic device on the low temperature extensive substrate such as glass, plastics, circuit or system.
Detailed description of the invention
Fig. 1 is people's structure high K dielectric membrane structure diagrammatic cross-section of the utility model,
It (a) is dielectric film entirety diagrammatic cross-section, wherein 1 is by the sub- film in 20-1000 period, sub-nanometer thickness
The composition of the periodically film of alternately stacked composition, each periodic unit is shown in Fig. 1 (b)-(d)；2 be the sub thin of low drain electric material
Film；3 be electric leakage flow barrier；
(b) a cycle cell schematics being made of the different sub- film of two kinds of dielectric properties, 4 be low drain electric material
Sub- film, 5 be the sub- film of high dielectric material；
(c) a cycle cell schematics being made of the different sub- film of three kinds of dielectric properties, 6 be that leakage current is minimum
Sub- film, 7 be the low sub- film of leakage current time, and 8 be leakage current highest, the highest sub- film of dielectric constant；
(d) a cycle cell schematics being made of the different sub- film of three kinds or more dielectric properties, sub- film is by leakage
Electric current from minimum to maximum again to secondary the smallest sequence successively lamination, or by forbidden bandwidth from minimum is up to again to secondary maximum
Sequence successively lamination, 9 be that leakage current is minimum or the widest sub- film of forbidden bandwidth, and 10 be that leakage current time is low or forbidden bandwidth time is wide
Sub- film, 11 be the sub- film that leakage current is higher or forbidden bandwidth is narrower, and 12 be that leakage current time is high or forbidden bandwidth time is narrow
Sub- film, 13 be leakage current highest or forbidden bandwidth is most narrow, the highest sub- film of dielectric constant.
Fig. 2 is the I-V curve of people's structure high K dielectric film MIM capacitor of the utility model embodiment.
Fig. 3 is the C-V curve of the human nature high K dielectric film MIM capacitor of the utility model embodiment.
Fig. 4 is the breakdown characteristic of people's structure high K dielectric film MIM capacitor of the utility model embodiment.
Fig. 5 is the TDDB characteristic of people's structure high K dielectric film MIM capacitor of the utility model embodiment.
Specific embodiment
With reference to the accompanying drawings and examples, the utility model is described in further detail, but the reality of the utility model
The mode of applying is not limited to this.
The utility model provides a kind of dielectric film of people's structure high dielectric constant, and by sub-nanometer thickness, (i.e. thickness is received less than 1
Rice) two kinds, three kinds, the different periodically alternately stacked composition of sub- film of even more than three kinds of dielectric property, generate Mike
Si Wei-wagner effect (Maxwell-Wagner), so that being formed has itself dielectric constant than this little film much higher
People's structure dielectric film (effective dielectric constant is 200 or more) of equivalent high dielectric constant, structure is as shown in Figure 1.It should be noted
It is that attached drawing 1 is using simplified form, non-accurate ratio, to achieve the purpose that aid in illustrating embodiment.
In the dielectric film of the utility model, at least one sub- film is low drain electric material, and at least another seed thin film is
High dielectric constant material.(leakage current density is less than 1 × 10 for low drain electric material-3A/cm2), hafnium oxide can be, but not limited to,
(HfOx), hafnium silicate (HfxSiOy), zirconium oxide (ZrOx), zirconium silicate (ZrxSiOy), gadolinium acid lanthanum (LaxGdOy), silica
(SiOx), silicon nitride (SiNx), silicon oxynitride (SiOxNy), tantalum oxide (TaOx) or dopant, alloy based on them
Or mixed crystal.High dielectric constant material (relative dielectric constant be greater than 30), can be, but not limited to, titanium oxide (TiOx),
One or more of SrTiOx, ZnOx or dopant, alloy or mixed crystal based on them.
As shown in Fig. 1 (b), for the dielectric film being made of the different sub- film of two kinds of dielectric properties, preparation method
Are as follows: using but be not limited to atomic layer deposition (ALD) or chemical vapor deposition (CVD) the method growth thickness in substrate and be less than
Then the sub- film of the first layer low drain electric material of 1nm is used but is not limited to ALD or CVD method and grows thickness on the sub- film
The sub- film of first layer high dielectric material of the degree less than 1nm, then ALD or CVD method are used but are not limited in the high dielectric of first layer
Growth thickness is less than the second layer low drain electric material of 1nm, the son of the material and first layer low drain electric material on the sub- film of material
Film it is identical；Then ALD is used but be not limited to again on second layer low drain electric material or CVD method growth thickness is less than 1nm
Second layer high dielectric material, the material is identical as the sub- film of first layer high dielectric material；According to above-mentioned steps repetitive operation,
Top layer's Low dark curient that ALD or the CVD method growth thickness on the sub- film of final high dielectric are less than 1nm is used but is not limited to again
Material eventually forms the people's structure high K dielectric film being periodically overlapped.
As shown in Fig. 1 (c) and 1 (d), for by three kinds or people's structure that more than the three kinds different sub- films of dielectric property are constituted
Property high K dielectric film, in each sub- film unit, from the bottom by leakage current from minimum to maximum again to secondary minimum
Sequence arrangement, or from the bottom by forbidden bandwidth from be up to it is minimum arranged again to secondary maximum sequence, as long as most bottom
Layer is the smallest sub- film of dielectric constant, and arrangement mode up is unlimited.Then in the same order by each unit
Superposition, i.e., the bottom of second unit are placed in the top layer of first unit.Therefore, on the basis of above-mentioned preparation method
On, the sub- film of each layer low drain electric material and high dielectric material is sequentially depositing from the bottom, every thickness degree is respectively less than 1nm, according to this
It is repeated cyclically, and guarantees top layer for the smallest sub- film that leaks electricity, to prepare by three kinds or more than three kinds of dielectric properties
People's structure high K dielectric film that different sub- films is constituted.Furthermore, it is possible to people's structure dielectric film lower surface,
Upper surface or the electric leakage barrier layer for distinguishing surface on it and lower surface one layer of a little nanometer thickness of deposition, can be obviously reduced its leakage
Electric current.
A kind of dielectric film of above-mentioned people's structure high dielectric constant can be used for SiC, GaN, InGaZnO or Si MOSFET,
Thin film transistor (TFT), oxygen grid or energy storage device.
Embodiment 1
A kind of HfOx/TiOx people's structure high K dielectric film (is numbered: SN-PSD_H.5T.5_100/ in attached drawing
H5), 250 DEG C at a temperature of,
A. with atomic layer deposition (ALD) method, growth thickness is in the monocrystal silicon substrate with 300nm thickness thermal oxide layer
The first layer hafnium oxide (HfOx) of 0.5nm；
B. with atomic layer deposition (ALD) method, growth thickness is the first layer titanium oxide of 0.5nm on first layer hafnium oxide
(TiOx)；
C. the second layer that growth thickness is 0.5nm on first layer titanium oxide with atomic layer deposition (ALD) method again aoxidizes
Hafnium,
D. it is aoxidized on second layer hafnium oxide with the second layer that atomic layer deposition (ALD) method growth thickness is 0.5nm again
Titanium,
E. it is repeated cyclically operation 100 times by the method for step a-d,
F. one layer of oxidation that growth thickness is 0.5nm on the titanium oxide of top layer with atomic layer deposition (ALD) method again
Hafnium；
G. finally stopped with the hafnium oxide electric leakage that Atomic layer deposition method grows one layer of 5nm thickness on the hafnium oxide of top layer
Layer.
So far HfOx/TiOx people's structure high K dielectric film of electrification flow barrier is formed.
I-V curve including people's structure high K dielectric film MIM capacitor in the present embodiment shown in Fig. 2, in order to than
Compared with Fig. 2-5 also provides 9nm thickness HfO2, 6nm thickness Al2O3With 150nm thickness AlOx/TiOx nano compound film (numbered in attached drawing:
SN-PSD_A.3T.7_150/A5 the individual features of MIM capacitor).It is normal including the high dielectric of people's structure in the present embodiment shown in Fig. 3
The C-V curve of number dielectric film MIM capacitor.By Fig. 2 and Fig. 3 as it can be seen that under 1V bias voltage, the 100nm of flow barrier is charged
The capacitance density of thick HfOx/TiOx people's structure film MIM capacitor can be up to 30.2fF/ ì m2, leakage current can be down to 2.1x10-5A/cm2。
It is thin that people's structure sub-nanometer periodic stack film of the utility model can be prepared into the good large area of uniformity
Film.Test result is also shown that the MIM capacitor prepared with HfOx/TiOx people's structure dielectric layer in above embodiments, and space is not
Uniformity only has~5%, illustrates that people's structure high K dielectric film provided by the utility model has good space equal
Even property.
Embodiment 2
A kind of HfOx/TiOx people's structure high K dielectric film (is numbered: SN-PSD_H.7T.3_100/ in attached drawing
H5), 250 DEG C at a temperature of,
A. with atomic layer deposition (ALD) method, growth thickness is in the monocrystal silicon substrate with 300nm thickness thermal oxide layer
The first layer hafnium oxide (HfOx) of 0.7nm；
B. with atomic layer deposition (ALD) method, growth thickness is the first layer titanium oxide of 0.3nm on first layer hafnium oxide
(TiOx)；
C. the second layer that growth thickness is 0.7nm on first layer titanium oxide with atomic layer deposition (ALD) method again aoxidizes
Hafnium,
D. it is aoxidized on second layer hafnium oxide with the second layer that atomic layer deposition (ALD) method growth thickness is 0.3nm again
Titanium,
E. it is repeated cyclically operation 100 times by the method for step a-d,
F. one layer of oxidation that growth thickness is 0.7nm on the titanium oxide of top layer with atomic layer deposition (ALD) method again
Hafnium；
G. finally stopped with the hafnium oxide electric leakage that Atomic layer deposition method grows one layer of 5nm thickness on the hafnium oxide of top layer
Layer.
So far HfOx/TiOx people's structure high K dielectric film of electrification flow barrier is formed.
I-V curve including people's structure high K dielectric film MIM capacitor in the present embodiment shown in Fig. 2.Shown in Fig. 3
C-V curve including people's structure high K dielectric film MIM capacitor in the present embodiment.It is by Fig. 2 and Fig. 3 as it can be seen that inclined in 1V
It sets under voltage, the capacitance density for charging 100nm thickness HfOx/TiOx people's structure film MIM capacitor of flow barrier can be up to
14.6fF/ìm2, leakage current can be down to 1.1x10-6A/cm2.Fig. 4 include in the present embodiment people's structure high K dielectric it is thin
The breakdown characteristic of film MIM capacitor, breakdown voltage 6.9V.Fig. 5 shows people's structure high dielectric constant of the present embodiment
The TDDB characteristic of dielectric film MIM capacitor, it is expected that being biased under 4.0V, the corresponding equivalent electric field of silica is 16.5Mv/cm
Service life was up to 10 years.
The embodiment 2 (numbering in attached drawing: SN-PSD_H.7T.3_100/H5) of the thickness of 100nm shown in Fig. 2-5,150nm are thick
AlOx/TiOx nano compound film (being numbered in attached drawing: SN-PSD_A.3T.7_150/A5) and 9nm thickness HfO2It (is compiled in attached drawing
Number: HfO2-9nm) capacitance density of MIM capacitor is suitable, but Fig. 2's -5 the results show that embodiment 2 breakdown voltage, TDDB longevity
Life is than commonly using high dielectric HfO2It is obviously high with AlOx/TiOx nano compound film MIM capacitor, also much lower normal of specific capacitance density
With high dielectric Al2O3MIM capacitor is obvious high (numbering in attached drawing: Al2O3-6nm), this illustrates people's structure provided by the utility model
Property high K dielectric film has better electricity, Mechanical Reliability.
Embodiment 3
A kind of HfOx/TiOx people's structure high K dielectric film with self-composed monomolecular electric leakage flow barrier,
250 DEG C at a temperature of,
A. with atomic layer deposition (ALD) method, growth thickness is in the monocrystal silicon substrate with 300nm thickness thermal oxide layer
The first layer hafnium oxide (HfOx) of 0.5nm；
B. with atomic layer deposition (ALD) method, growth thickness is the first layer titanium oxide of 0.5nm on first layer hafnium oxide
(TiOx)；
C. the second layer that growth thickness is 0.5nm on first layer titanium oxide with atomic layer deposition (ALD) method again aoxidizes
Hafnium,
D. it is aoxidized on second layer hafnium oxide with the second layer that atomic layer deposition (ALD) method growth thickness is 0.5nm again
Titanium,
E. it is repeated cyclically operation 100 times by the method for step a-d,
F. one layer of oxidation that growth thickness is 0.5nm on the titanium oxide of top layer with atomic layer deposition (ALD) method again
Hafnium；
G. finally use unimolecule self assembly deposition method on the hafnium oxide of top layer with the positive octadecyl ester self assembly one of phosphoric acid
Layer unimolecule electric leakage barrier layer.
So far HfOx/TiOx people's structure high K dielectric film with self-composed monomolecular current barrier layer is formed.
Embodiment 4
A kind of ZrOx/HfOx/TiOx people's structure high K dielectric film, 250 DEG C at a temperature of,
A. with atomic layer deposition (ALD) method, growth thickness is in the monocrystal silicon substrate with 300nm thickness thermal oxide layer
The first layer zirconium oxide (ZrOx) of 0.3nm；
B. with atomic layer deposition (ALD) method, growth thickness is the first layer of 0.3nm on first layer zirconium oxide (ZrOx)
Hafnium oxide (HfOx)；
C. with atomic layer deposition (ALD) method, growth thickness is the first layer titanium oxide of 0.4nm on first layer hafnium oxide
(TiOx)；
D. the second layer that growth thickness is 0.3nm on first layer titanium oxide with atomic layer deposition (ALD) method again aoxidizes
Zirconium；
E. the second layer that growth thickness is 0.3nm on second layer zirconium oxide with atomic layer deposition (ALD) method again aoxidizes
Hafnium；
F. it is aoxidized on second layer hafnium oxide with the second layer that atomic layer deposition (ALD) method growth thickness is 0.4nm again
Titanium；
G. operation 50 times is repeated cyclically by the method for step a-f；
H. one layer of oxidation that growth thickness is 0.3nm on the titanium oxide of top layer with atomic layer deposition (ALD) method again
Hafnium；
I. one layer of oxidation that growth thickness is 0.3nm on the hafnium oxide of top layer with atomic layer deposition (ALD) method again
Zirconium；
J. finally stopped with the zirconium oxide electric leakage that Atomic layer deposition method grows one layer of 5nm thickness on the zirconium oxide of top layer
Layer.
So far ZrOx/HfOx/TiOx people's structure high K dielectric film of electrification flow barrier is formed.
Above embodiments are illustrated only for the purposes of explanation, the rights protection scope being not intended to limit the utility model,
Those skilled in the art under the premise of not departing from the utility model principle, technology and range it is made it is any change and repair
Decorations, in the protection scope all asked described in the utility model.The rights protection scope described in the utility model asked is wanted with right
It asks subject to book.
Claims (4)
1. a kind of dielectric film of people's structure high dielectric constant, which is characterized in that the dielectric film includes multiple periodically overlappings
Sub- film unit, every sub- film unit overlaps by the sub- film of low drain electric material and the sub- film of high dielectric material,
The thickness of each straton film is respectively less than 1nm；The bottom of the dielectric film and top layer are that the son of low drain electric material is thin
Film；The sub- film of the low drain electric material is using one or more kinds of different materials；The sub- film of the high dielectric material uses
One or more kinds of different materials；When the dielectric film uses a variety of different materials, in every sub- film unit, each son is thin
Film is first incremented by the sequence successively decreased again by leakage current by the bottom and arranged, or the sequence arrangement for first successively decreasing again incremental by forbidden bandwidth.
2. a kind of dielectric film of people's structure high dielectric constant according to claim 1, which is characterized in that every sub- film
In unit, the sub- film of the bottom is the smallest sub- film of dielectric constant.
3. a kind of dielectric film of people's structure high dielectric constant according to claim 1 or 2, which is characterized in that given an account of
The lower surface of conductive film, upper surface or surface and lower surface are equipped with the electric leakage flow barrier of one layer of a little nanometer thickness on it respectively.
4. a kind of dielectric film of people's structure high dielectric constant according to claim 3, which is characterized in that the leakage current
Barrier layer uses inorganic oxide material or organic self assembled monolayer material.
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