CN105837799A - Dicarbonyl bridged pyrrolo-pyrrole-dione polymer as well as preparation method and application thereof - Google Patents
Dicarbonyl bridged pyrrolo-pyrrole-dione polymer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dicarbonyl bridged pyrrolo-pyrrole-dione polymer as well as a preparation method and application thereof. The structural formula of the dicarbonyl bridged pyrrolo-pyrrole-dione polymer is shown by formula I. As shown in the formula I, R is selected from any one of C5-C80 (preferably C5-C50) linear or branched alkyl, and n is a polymerization degree that is 5-200. The invention also provides a preparation method of the polymer shown by the formula I. The synthetic route of the polymer disclosed by the invention is simple and feasible, is few in synthetic step, and is suitable for large-scale synthesis. The mobility ratio and on-off ratio of a field-effect transistor prepared by taking the dicarbonyl bridged pyrrolo-pyrrole-dione polymer disclosed by the invention as an organic semiconductor layer are relatively high, the mobility ratio is 0.54cm<2>V<-1>s<-1>, and the on-off ratio is greater than 10<6>. The polymer disclosed by the invention has a good application prospect in an organic field-effect device.
Description
Technical field
The invention belongs to organic semiconducting materials technical field, be specifically related to a class dicarbapentaborane bridging pyrrolo-pyrrole-dione
Polymer and preparation method and application.
Background technology
Organic field effect tube (Organic Field-effect Transistors is called for short OFETs) is with organic semiconductor
Material is carrier blocking layers, is controlled the active device of materials conductive ability by electric field, is based on pi-conjugated molecule
Unique construction features and abundant physicochemical properties and derivative important application.High-performance OFETs has wide
Application prospect, it is in fields such as smart card, sensor, electronic radio frequency tags, large screen display and integrated circuits
Successful Application necessarily can promote the technological innovation of the numerous areas such as information, the energy, life, will be to economic development
And social progress produces far-reaching influence.Compared with traditional inorganic material, it is wide that organic semiconducting materials has raw material
The advantages such as general and synthesis technique is simple, have again simultaneously the Modulatory character of physicochemical properties and good elasticity and
Pliability, available solwution method is processed, thus for manufacturing lightweight on a large scale, flexible electronic device provides possibility.
Just because of this, just by researcher and the extensive concern of industrial circle since it is born, correlational study has become as
One of focus of organic electronics research field.
Organic semiconductor layer is the core of OFET device, and its character decides the performance of fieldtron.Cause
The semi-conducting material that this designs, synthesis performance is excellent is the wide variety of basis of organic field effect tube and premise.Have
The performance parameter of field effect transistors mainly includes mobility (μ), on-off ratio (Ion/Ioff) and threshold voltage (VT)。
Wherein mobility (μ) and on-off ratio (Ion/Ioff) numerical value the biggest, indicate that device has a preferable performance, and threshold
Threshold voltage (VTH) to be then closer to zero volt the best, such device more can save the energy.It addition, field effect
The whether simple of the preparation condition of device is also to weigh its whether excellent important indicator.Organic field effect tube is permissible
Prepared by solwution method technique low cost, large area such as spraying, rejection film and printings.
Organic semiconductor layer active material used by organic field effect tube can be to include the little molecule of machine and polymer
Semi-conducting material etc..Wherein, polymer semiconducting material has the features such as simple, the good film-forming property of synthesis, thus has
Bigger application prospect.So research and development high-performance polymer semi-conducting material has become as the focus of this area,
The most also huge progress is obtained.But, the property such as mobility of existing polymer field effect transistor device
Still can not meeting wide variety of needs, being of great significance so continuing Development of Novel polymeric material tool,
The achievement in research the most also to our development with independent intellectual property right provides opportunity with seizing science and technology commanding elevation.
Summary of the invention
It is an object of the invention to provide class dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer and preparation method thereof and answer
With.
The dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer that the present invention provides, its general structure is as shown in formula I:
In described Formulas I, R is selected from C5-C80Straight or branched alkyl in any one；
N is 5-200.
Concrete, in described Formulas I, R is selected from C10-C50Straight or branched alkyl in any one, be chosen in particular from
C10-C30Straight or branched alkyl in any one, more specifically 2-decyl dodecyl or the 4-decyl tetradecane
Base；
N is 10-100, specially 17 or 19.
More specifically, polymer shown in described Formulas I is PDTO-1 (R=2-decyl dodecyl) or PDTO-2 (R=4-
Decyl myristyl).
What the present invention provided prepares the method for polymer shown in described formula I, comprises the steps:
Under conditions of palladium catalyst exists, compound shown in formula IV, part are carried out Suzuki with compound shown in formula VIII
Polyreaction, reacts complete and obtains polymer shown in described formula I；
In described Formula VIII, the definition of R is identical with the R definition in described Formulas I.
In said method, described palladium catalyst is in three (dibenzalacetone) two palladium and tetrakis triphenylphosphine palladium
At least one；
Described part is three (o-tolyl) phosphine or triphenylphosphines；
Compound shown in described formula IV is 1:0.95～1.05 with the molar ratio of compound shown in formula VIII, specially 1:
1；The consumption of described palladium catalyst is that compound shown in described formula IV feeds intake the 1%～10% of mole dosage, specially 5%；
The consumption of described part is that compound shown in described formula IV feeds intake the 10%～50% of mole dosage, specially 30%；
In described Suzuki polymerization procedure, temperature is 90 DEG C～150 DEG C, preferably 80 DEG C～100 DEG C, specially 90 DEG C；
Time is 5 hours～72 hours, preferably 24 hours；
Described Suzuki polyreaction is carried out in an inert atmosphere；Described inert atmosphere concretely argon gas atmosphere；
Described reaction is carried out in a solvent；Described solvent is chosen in particular from least one in toluene and chlorobenzene.The use of solvent
Measure and be as the criterion being completely dissolved reactant.Above-mentioned prepare the synthetic route of compound shown in formula I and formula IV as shown in Figure 1.
Described method may also include following purification step:
After described polyreaction, add, after gained reaction system being cooled down, the mixture being made up of methanol and hydrochloric acid,
Agitation and filtration under room temperature, respectively extracts 12 hours with methanol, acetone, normal hexane successively by gained solid apparatus,Soxhlet's,
Extract with chlorobenzene afterwards；Wherein, in the described mixture being made up of methanol and hydrochloric acid, the volume ratio of methanol and hydrochloric acid is concrete
Can be 20:1, the concentration of hydrochloric acid concretely 6M.
It addition, polymer application in preparing organic effect transistor shown in the described formula I that provides of the invention described above and
With the polymer organic field effect tube as organic semiconductor layer shown in described formula I, fall within the protection model of the present invention
Enclose.Wherein, the thickness of described organic semiconductor layer is 10-50nm, specially 30nm.
It is an advantage of the current invention that:
1, the synthesis material of this novel dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer can simply synthesize or from
Commercial sources is purchased in a large number and is obtained, and is suitable for extensive synthesis.
2, this novel dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer has wider uv-visible absorption spectroscopy,
Excellent thermal stability, good film property, it is expected to prepare high-performance polymer field-effect transistor by solwution method
Device.
3, this novel dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer is field-effect transistor tool prepared by semiconductor layer
There are higher carrier mobility (μ) and on-off ratio (Ion/Ioff) (μ is up to 0.54cm2V-1s-1, Ion/IoffFor
106-107), there is good commercial application prospect.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer shown in formula I of the present invention.
Fig. 2 is the embodiment of the present invention 1, the synthetic route chart of polymer P DTO-1 and PDTO-2 described in 2.
Fig. 3 is the embodiment of the present invention 1, polymer P DTO-1 described in 2 and the ultraviolet-visible of PDTO-2 chlorobenzene solution
Abosrption spectrogram.Absorbance (a.u.): normalization absorption intensity；Wavelength (nm): wavelength (nanometer).
Fig. 4 is the embodiment of the present invention 1, polymer P DTO-1 described in 2 and the ultraviolet-ray visible absorbing of PDTO-2 thin film
Spectrogram.Absorbance (a.u.): normalization absorption intensity；Wavelength (nm): wavelength (nanometer).
Fig. 5 is the embodiment of the present invention 1, the thermal gravimetric analysis curve figure of polymer P DTO-1 and PDTO-2 described in 2.
Weight (wt%): mass percent；Temperature(oC): temperature (degree Celsius).
Fig. 6 is the embodiment of the present invention 1, the cyclic voltammetry curve chart of polymer P DTO-1 and PDTO-2 described in 2.
Current (mA): electric current (milliampere)；Potential (V): voltage (volt).
The structural representation of the polymer effect transistor that Fig. 7 provides for the present invention.Wherein Au: gold；Si: silicon；SiO2:
Silicon dioxide；OTS: octadecyl trichlorosilane alkane；Organic semiconductor: polymer (PDTO-1 or
PDTO-2)。
Fig. 8 turns for the output of representative polymer PDTO-1 provided with the present invention and PDTO-2 field-effect transistor
Move performance diagram and output characteristic curve figure；Wherein, | IDS 1/2|[A]1/2: | electric current |1/2[ampere]1/2；VG[V]: grid voltage [volt
Special]；IDS[A]: electric current [ampere]；VDS[V]: source-drain voltage [volt].
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following example.Institute
Method of stating is conventional method if no special instructions.Described raw material the most all can obtain from open commercial sources
?.
Reaction substrate 1 used in following embodiment commercially obtains, reaction substrate 3a and 3b reference literature
Adv.Mater.2012,24,4618-4622 synthesis, reaction substrate, solvent and catalyst used by remaining all can be from business ways
Footpath obtains.
Embodiment 1, polymer P DTO-1 synthesis (R=2-decyl dodecyl in formula I) (its synthetic route such as figure
Shown in 2)
1) synthesis of double (the 5-bromothiophene base) ethane-1,2-diketone (2) of the compound 1,2-of ownership formula IV
Will be equipped with 1,2-bis-(2-thienyl) ethane-1,2-diketone (2.0 grams, 10 mMs), sodium bicarbonate (3.4 grams,
40 mMs) chloroform (40 milliliters) solution be slowly added dropwise after being cooled to 0 DEG C bromine (2.0 milliliters, 40 milli
Mole).After completing, reaction system, under argon shield, is heated to 60 DEG C of stirring reactions 4 hours.It is cooled to room temperature
In falling back and with chloroform extraction three times, decompression removes gained solid residues recrystallization, institute after organic solvent
Obtain yellow solid and be dried to obtain target product 2.2 grams under room temperature in vacuum conditions.Productivity: 58%.
Structural characterization data are as follows:
Mass spectrum: HRMS (m/z): [M]+:379.7994.。
Hydrogen is composed:1H NMR(300MHz,CDCl3) δ (ppm): 7.90 (d, J=4.2Hz, 2H), 7.19 (d, J=4.2
Hz, 2H). carbon is composed:13C NMR(75MHz,CDCl3)δ(ppm):179.3,137.7,131.7,128.1.
2) synthesis of the compound 4a of ownership formula VIII
Will be equipped with 3a (973 milligrams, 1.0 mMs), 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxanes penta
Borine (0.6 milliliter, 3.0 mMs), the solution of oxolane (20 milliliters) are cooled to-20 DEG C, in argon shield
Lower dropping lithium diisopropylamine (1.2 milliliters, 2.4 mMs), after be to slowly warm up to 0 DEG C continue reaction 1h.With full
Reacting with aqueous ammonium chloride solution cancellation, dichloromethane extracts, the dried recrystallization of anhydrous sodium sulfate under vacuum
It is dried to obtain red solid (845 milligrams).Productivity: 69%.
Structural characterization data are as follows:
Mass spectrum: HRMS (m/z): [M]+:1225.9332.
Hydrogen is composed:1H NMR(300MHz,CDCl3) δ (ppm): 8.91 (d, J=3.9Hz, 2H), 7.71 (d, J=3.9
Hz, 2H), 4.96 (d, J=7.5Hz, 4H), 1.89 (br, 2H), 1.37 (s, 24H), 1.21 (br, 80H), 0.89 (m,
12H). carbon is composed:13C NMR(75MHz,CDCl3)δ(ppm):161.8,140.5,137.7,136.1,135.7,1088,
84.6,46.3,37.8,31.9,31.3,30.0,29.7,29.66,29.59,29.36,26.35,24.8,22.7,14.1.
2) synthesis of the polymer P DTO-1 of ownership Formulas I
By the compound 1 of ownership formula IV, double (5-bromothiophene base) ethane-1 of 2-, 2-diketone (2) (76.0 milligrams, 0.20 milli
Mole) and ownership formula VIII (R is 2-decyl dodecyl) compound 4a (245.0 milligrams, 0.20 mM), palladium
Catalyst three (dibenzalacetone) two palladium (9.0 milligrams, 0.01 mM), part three (o-tolyl) phosphine (19
Milligram, 0.06 mM), the aqueous solution of 2M potassium carbonate 2.0 milliliters and solvent toluene (6.0 milliliters) join reaction
In Ping, argon carries out low temperature deoxygenation post-heating to 90 DEG C argon shield and carries out polyreaction 24 hours.After cooling,
Add 200 ml methanol/6M HCl mixture (volume ratio 20:1), stir 2 hours under room temperature, filter.Obtain
Solid purify with apparatus,Soxhlet's, extraction solvent respectively extracts 12 hours for methanol, acetone, normal hexane successively, uses afterwards
Chlorobenzene extracts and obtains subject polymer 205 milligrams, yield 85%.
Structural characterization data are as follows:
Molecular weight: GPC:Mn=19.8kDa, Mw=46.1kDa, PDI=2.32.n are 17；
Elementary analysis: C72H108N2O4S4, value of calculation: C, 72.43；H,9.12；N,2.35；Probe value: C 73.22,
H 9.32,N 2.13.。
Learn that from above this compound structure is correct, for polymer P DTO-1.
Embodiment 2, polymer P DTO-2 synthesis (R=4-decyl myristyl in formula I) (its synthetic route such as figure
Shown in 2)
1) synthesis of the compound 2 of ownership formula IV
The synthesis of compound 2 is carried out with reference to embodiment 1.
1) synthesis of the compound 4b of ownership formula VIII
Will be equipped with 3b (973 milligrams, 1.0 mMs), 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxanes penta
Borine (0.6 milliliter, 3.0 mMs), the solution of oxolane (20 milliliters) are cooled to-20 DEG C, in argon shield
Lower dropping lithium diisopropylamine (1.2 milliliters, 2.4 mMs), after be to slowly warm up to 0 DEG C continue reaction 1h.With full
Reacting with aqueous ammonium chloride solution cancellation, dichloromethane extracts, the dried recrystallization of anhydrous sodium sulfate under vacuum
It is dried to obtain red solid (796 milligrams).Productivity: 65%.
Structural characterization data are as follows:
Mass spectrum: HRMS (m/z): [M]+:1225.9324.
Hydrogen is composed:1H NMR(300MHz,CDCl3) δ (ppm): 9.02 (d, J=3.9Hz, 2H), 7.71 (d, J=3.9
Hz, 2H), 4.11 (d, J=7.5Hz, 4H), 1.69 (br, 4H), 1.37 (s, 24H), 1.23-1.21 (br, 78H), 0.89 (m,
12H). carbon is composed:13C NMR(75MHz,CDCl3)δ(ppm):161.4,140.0,137.9,136.3,135.6,108.5,
84.6,42.5,37.14,33.5,31.9,30.5,30.1,29.72,29.67,29.64,29.36,27.1,26.6,24.8,22.7,
14.1.
2) synthesis of the polymer P DTO-2 of ownership Formulas I
By the compound 1 of ownership formula IV, double (5-bromothiophene base) ethane-1 of 2-, 2-diketone (2) (76.0 milligrams, 0.20 milli
Mole) and ownership formula VIII (R is 4-decyl myristyl) compound 4b (245.0 milligrams, 0.20 mM), palladium
Catalyst three (dibenzalacetone) two palladium (9.0 milligrams, 0.01 mM), part three (o-tolyl) phosphine (19
Milligram, 0.06 mM), the aqueous solution of 2M potassium carbonate 2.0 milliliters and solvent toluene (6.0 milliliters) join reaction
In Ping, argon carries out low temperature deoxygenation post-heating to 90 DEG C argon shield and carries out polyreaction 24 hours.After cooling,
Add 200 ml methanol/6M HCl mixture (volume ratio 20:1), stir 2 hours under room temperature, filter.Obtain
Solid purify with apparatus,Soxhlet's, extraction solvent respectively extracts 12 hours for methanol, acetone, normal hexane successively, uses afterwards
Chlorobenzene extracts and obtains subject polymer 209 milligrams, yield 88%.
Structural characterization data are as follows:
Molecular weight: GPC:Mn=22.4kDa, Mw=55.5kDa, PDI=2.48.n are about 19；
Elementary analysis: C72H108N2O4S4, value of calculation: C, 72.43；H,9.12；N,2.35；Probe value: C 72.87,
H 9.29,N 2.08.。
Learn that from above this compound structure is correct, for polymer P DTO-2.
Embodiment 3, the spectrum property of polymer P DTO-1 and PDTO-2
Fig. 3 and Fig. 4 is polymer P DTO-1 and PDTO-2 chlorobenzene solution and the thin film of embodiment 1 and 2 preparation
Uv-visible absorption spectra figure.
From the figure 3, it may be seen that this base polymer is in UV-visible region, even near infrared region presents and absorbs more by force, explanation
Polymer molecule has stronger Intramolecular electron transfer.
As shown in Figure 4, these two kinds of polymer present more strongly-ordered gathering in solids or assemble in order.
Embodiment 4, the thermal property of polymer P DTO-1 and PDTO-2
Fig. 5 is embodiment 1, the thermogravimetric curve of polymer P DTO-1 and PDTO-2 of 2 preparations.
As shown in Figure 5, polymer P DTO-1 and PDTO-2 decomposition temperature (5% loss) are respectively 380 and 391 DEG C,
Illustrate that this base polymer has good thermal stability.
Embodiment 5, the electrochemical properties of polymer P DTO-1 and PDTO-2
Fig. 6 is embodiment 1, the cyclic voltammetry curve of polymer P DTO-1 and PDTO-2 of 2 preparations.
The electrochemical properties of polymer is tested by cyclic voltammetric device.Poly-with formed in drop film method to platinum electrode
Compound thin film is as test object.Test uses traditional three-electrode system, wherein with platinum rod, platinum filament, silver/silver chloride
Respectively work click, to electrode and reference electrode, with the anhydrous acetonitrile of tetrabutyl hexafluorophosphoric acid ammonium salt for supporting
Electrolyte.Sweep limits is-1.4～1.6 volts (vs.Ag/AgCl), sweep speed be 100 millivolts per second.
From Fig. 6 learn the initial oxidation current potential of polymer P DTO-1 and PDTO-2 1.13 and 1.15V, thus
Estimating that their HOMO energy level is respectively-5.53 and-5.55 electron-volts, their initial reduction current potential is simultaneously
-0.76 and-0.73V.Can be evaluated whether that their lumo energy is respectively-3.64 and-3.67 electron-volts.
Embodiment 6, the field-effect transistor preparation of polymer P DTO-1 and PDTO-2 and performance.
Fig. 7 is the structural representation of polymer field effect transistor, as it can be seen, use highly doped silicon chip as lining
The end, gate electrode, the silicon dioxide of 300 nanometer thickness is as insulating barrier, and gold is source electrode and drain electrode.Silicon dioxide is adopted
Modify with phenyl trichlorosilane, prepare, by rejection film method, the organic semiconductor layer that thickness is 30 nanometers, and at air
In in thermal station 120 degrees Celsius anneal 5 minutes, obtain polymer field effect field effect transistor devices.
Fig. 8 is transfer curve and the curve of output of the field-effect transistor prepared by polymer P DTO-1 and PDTO-2.
Such device has good field effect performance of control as seen from the figure.Carrier mobility can be drawn by Equation for Calculating:
IDS=(W/2L) Ciμ(VG–VT)2(sat.,VDS=VG–VT)
Wherein, IDSFor drain current, μ is carrier mobility, VGFor grid voltage, VTFor threshold voltage, W is
Channel width (W=1400 micron), L is channel length (L=50 micron), CiFor insulator electric capacity (Ci=7.5 × 10-9
Method every square centimeter).Utilize (IDS, sat)1/2To VGMapping, and makees linear regression, can the slope of the thus regression line
Extrapolate carrier mobility (μ), the section of the regression line Yu X-axis try to achieve VT.The polymerization of preparation in above-mentioned each example
The device performance of thing field-effect transistor is as shown in table 1.
On-off ratio can be drawn by the ratio of the maxima and minima of Fig. 8 source-drain current.
Make more than 20 organic field effect tube devices with PDTO-1 and PDTO-2 for semiconductor layer, this
A little device performances are stable, and its representational performance parameter is as shown in table 1:
Table 1, the device performance of field-effect transistor
All of test result indicate that, dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer shown in the Formulas I that the present invention provides
It it is excellent polymer semiconducting material.The present invention is not limited to reported PDTO-1 and PDTO-2 two kinds polymerization
Thing material, changes different substituent R and can obtain the novel dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer of series,
And synthetic route that the present invention is given is simple, synthesis step is few, is suitable for extensive synthesis.This is for grinding further
Send out high performance polymer semi-conducting material and there is important directive significance.
Claims (10)
1. polymer shown in Formulas I:
In described Formulas I, R is selected from C5-C80Straight or branched alkyl in any one；
N is 5～200.
Polymer the most according to claim 1, it is characterised in that: in described Formulas I, R is selected from C10-C50's
Any one in straight or branched alkyl, is chosen in particular from C10-C30Straight or branched alkyl in any one,
More specifically 2-decyl dodecyl or 4-decyl myristyl；
N is 10-100, specially 17 or 19.
3. prepare a method for polymer shown in the arbitrary described Formulas I of claim 1 or 2, comprise the steps:
Under conditions of palladium catalyst exists, by compound and potassium carbonate shown in compound shown in formula IV, part, formula VIII
Aqueous solution carry out Suzuki polyreaction, react complete and obtain polymer shown in described formula I；
In described Formula VIII, the definition of R is identical with the R definition in Formulas I described in claim 1.
Method the most according to claim 3, it is characterised in that: described palladium catalyst is selected from three (dibenzylidenes
Acetone) at least one in two palladiums and tetrakis triphenylphosphine palladium；
Described part is three (o-tolyl) phosphine or triphenylphosphines.
5. according to the method described in claim 3 or 4, it is characterised in that: compound shown in described formula IV and formula VIII
The molar ratio of shown compound is 1:0.95～1.05, specially 1:1；
The consumption of described palladium catalyst is that compound shown in described formula IV feeds intake the 1%～10% of mole dosage, specially 5%；
The consumption of described part is that compound shown in described formula IV feeds intake the 10%～50% of mole dosage, specially 30%；
The concentration of the aqueous solution of described potassium carbonate is 2M；The aqueous solution of described potassium carbonate and compound shown in described formula IV
Amount ratio be 2.0 milliliters: 0.20 mM.
6. according to described method arbitrary in claim 3-5, it is characterised in that: described Suzuki polyreaction walks
In Zhou, temperature is 90 DEG C～150 DEG C, preferably 80 DEG C～100 DEG C, specially 90 DEG C；
Time is 5 hours～72 hours, specially 24 hours.
7. according to described method arbitrary in claim 3-6, it is characterised in that: described Suzuki polyreaction exists
Inert atmosphere is carried out；
Described inert atmosphere concretely argon gas atmosphere；
The reaction of described Suzuki polyreaction is carried out in a solvent；
Described solvent is chosen in particular from least one in toluene and chlorobenzene.
8. polymer application in preparing organic effect transistor shown in the arbitrary described formula I of claim 1 or 2.
9. an organic field effect tube, it is characterised in that: in described organic field effect tube, constitute organic
The material of semiconductor layer is polymer shown in the arbitrary described Formulas I of claim 1 or 2.
Organic field effect tube the most according to claim 9, it is characterised in that: described organic semiconductor layer
Thickness be 10-50nm, specially 30nm.
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