CN107974667B - A kind of method of quick measurement sequential keyboard encoder ALD presoma critical pulse width - Google Patents
A kind of method of quick measurement sequential keyboard encoder ALD presoma critical pulse width Download PDFInfo
- Publication number
- CN107974667B CN107974667B CN201711222641.1A CN201711222641A CN107974667B CN 107974667 B CN107974667 B CN 107974667B CN 201711222641 A CN201711222641 A CN 201711222641A CN 107974667 B CN107974667 B CN 107974667B
- Authority
- CN
- China
- Prior art keywords
- precursor
- ald
- pulse width
- film
- width
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000005259 measurement Methods 0.000 title claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 84
- 238000000151 deposition Methods 0.000 claims abstract description 42
- 230000008021 deposition Effects 0.000 claims abstract description 38
- 238000012545 processing Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 9
- 230000008859 change Effects 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000011261 inert gas Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000010349 pulsation Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000004590 computer program Methods 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000000231 atomic layer deposition Methods 0.000 description 68
- 239000010408 film Substances 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003380 quartz crystal microbalance Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 210000001367 artery Anatomy 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- 206010000125 Abnormal dreams Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
Abstract
Present invention discloses a kind of methods of quickly measurement sequential keyboard encoder ALD presoma critical pulse width, and depositing an independent film sample by ALD processing procedure can determine the presoma critical pulse width of used sequential keyboard encoder ALD processing procedure；In the method, ALD precursor gas pulse width t can by controlling change: precursor A gas pulses width t is gradually increased from length is short to, quality knots modification Δ m of the obtained film in the specified deposition cycle of each precursor A gas pulses width t is measured by QCM, the functional relation for finally obtaining each film quality incrementss Δ m Yu precursor gas pulse width t analyzes the functional relation of obtained Δ m and t to determine the ALD precursor A critical pulse width of used sequential keyboard encoder ALD processing procedure.Whole measurement process, which only needs to deposit a film sample, can measure presoma critical pulse width, and the presoma of required consumption also greatly reduces, and the testing time greatly shortens.
Description
Technical field
The present invention relates to a kind of methods of quickly measurement sequential keyboard encoder ALD presoma critical pulse width.
Background technique
ALD (atomic layer deposition, Atomic layer deposition) utilizes surface saturated reaction (surface
Saturation reactions) realize thin-film material by atomic layer growth, in a certain range to temperature and reactant
The variation of flux is insensitive.Atomic layer deposition and common chemical deposition have similarity.But in atomic layer deposition process, newly
The chemical reaction of one layer of atomic film is that directly preceding layer is associated therewith, and this mode makes each reaction only deposit one layer of original
Son.Even if the unique surface response feature of atomic layer deposition reduces normal chemical vapor deposition to temperature, pressure and component
It is strict with, there is still a need for the parameters of optimization ALD to realize its accurate thickness control and super shape-retaining ability by people.In timing
In formula ALD processing procedure, presoma threshold dose is one of the important parameter for controlling surface saturation.
In ALD technique, absorption is generally the chemisorption of monolayer.Usually described using Langmuir model.
In this model, Langmuir has made several hypothesis:
1) surface of solids be homogeneous, it is flat；
2) surface of solids has a certain number of points (position) for adsorption molecule attachment；
3) all these points are all equivalents；
4) each point can only adsorb a molecule (only forming monolayer covering)；
5) it is adsorbed between the molecule of the surface of solids and does not interact.
Under these premises, when adsorption and de-adsorption reaches balance, basic Langmuir can be easily derived
Equation:Herein, θAFor the gas molecule the surface of solids coverage rate；Keq AFor a constant, with suction
Attached, desorption rate is related；PAFor the air pressure of the adsorbate.
In basic Langmuir equation, work as COEFFICIENT Keq AWhen being worth different, curve shows the characteristic of " soft " and " hard ", such as
Shown in Fig. 1.Obviously, Keq AValue is bigger, and curve gets over " hard ", easier to reach saturation adsorptive value.In addition, it is obvious that grown in ALD
In, precursor molecule coverage rate will directly determine deposition rate.And presoma air pressure can be by the amount in feeding source in reaction chamber
Determine, can by impulse valve opening time length depending on.Ideally, the impulse valve opening time tends to be infinite, forerunner
Body gas molecule can be only achieved 100% in the coverage rate of substrate surface
In practical applications, it is generally recognized that when the impulse valve opening time is more than a certain particular value, precursor gas molecule
Reaching a corresponding particular value in the coverage rate of substrate surface, (for example, coverage rate reaches 98% or 99%, this value can basis
Actual needs and select), we be think that precursor gas molecule has been nearly completed all standing in substrate surface, at this time we
That is this impulse valve opening time critical pulse width for being referred to as corresponding presoma.In practice, it is often found that pulse valve
After the door opening time reaches certain value, molecule is basicly stable in the coverage rate of substrate surface and is difficult to find big change
Change.
Every a pair of combinations of reactants and specific ALD deposition equipment, all correspond to the critical arteries and veins of presoma of respective ALD processing procedure
Rush width.Therefore, during developing new ALD technique, the presoma critical pulse width of corresponding ALD processing procedure is found, is
An essential process.The method of traditional searching presoma critical pulse width, is carried out with following process:
A temperature value is selected in ALD-window, is carried out the growth of ALD film, is set a precursor gas arteries and veins every time
It rushes width value progress ALD to grow to obtain a sample, selects a series of precursor gas pulse width values, it is a series of right to obtain
The film sample answered is measured using HRTEM high resolution transmission electron microscope, elliptic polarization spectrometer, step instrument etc.
The film thickness arrived, deposition rate are obtained by formula GPC=film thickness/growth loop number.When obtaining each forerunner
After the corresponding GPC of gas pulse width value, GPC~precursor gas pulse width values relationship is obtained, its ALD presoma is analyzed
Critical pulse width.
It should be evident that this traditional method, the consuming time is too long, time-consuming and laborious.It is generally completed entire test about
Two weeks or more is needed, a large amount of manpower and material resources are expended.Long-term is repeated same substrate cleaning, also causes high effort for.When
When arrive tens, nearly hundred film samples, using HRTEM high resolution transmission electron microscope, elliptic polarization spectrometer,
Step instrument etc. is come the thickness of such a large amount of film sample measured and the bad dream of tester.
Summary of the invention
In order to overcome various defects of the existing technology, shorten measurement sequential keyboard encoder ALD presoma critical pulse width
Time-consuming reduces test job amount, reduces test required cost, and the invention proposes a kind of completely new quick measurement ALD presomas
The method of critical pulse width.
The method of quick measurement ALD presoma critical pulse width proposed by the present invention, is characterized in that:
The ALD presoma critical pulse width is related to the parameter of used presoma, ALD equipment；
Depositing an independent film sample by ALD processing procedure can determine the presoma of used sequential keyboard encoder ALD processing procedure
Critical pulse width；Including a precursor A gas pulses, a precursor B in single growth circulation in sequential keyboard encoder ALD processing procedure
Gas pulses, two inert purge gas pulses；
In the method, ALD precursor gas pulse width t can by controlling change；
In the ALD equipment used in deposition film sample, configured with for monitoring film that ALD deposition obtains in real time
The QCM (Quartz Crystal Microbalance, quartz crystal microbalance) of quality incrementss Δ m, in measurement ALD forerunner
During body critical pulse width, the vessel temp of each presoma, ALD deposition temperature, that is, vacuum reaction chamber temperature, inertia
Gas bleed pulse width, the flow velocity of inert gas, matched another precursor B gas pulses width remain unchanged, and
Precursor A gas pulses width t is gradually increased from length is short to, and measures obtained film in each precursor A gas by QCM
Quality knots modification Δ m in the specified deposition cycle of body pulse width t finally obtains each film quality incrementss Δ m with before
The functional relation for driving gas pulse width t, analyzes the functional relation of the Δ m and t to determine used sequential keyboard encoder ALD processing procedure
ALD presoma critical pulse width；
The quickly method of measurement sequential keyboard encoder ALD presoma critical pulse width, specifically comprises the following steps:
A. sample and sample introduction are prepared:
The substrate material of cleaning is dried up with inert gas, is placed into substrate pallet；Pallet is moved into together with substrate
Vacuum reaction chamber is opened vacuum pump, is vacuumized to vacuum reaction chamber；
B. ALD technological parameter is set:
It sets film deposition temperature T, precursor A temperature, precursor B temperature, inert gas and rinses pulse width, presoma
A gas pulses width initial value tAlow, it is precursor B gas pulses width, precursor A gas pulses width incremental steps Δ t, heavy
Cycle-index N, deposition outer circulation number M, measurement relative error limit in product, face for the ALD deposition and measurement ALD presoma of film
Boundary's pulse width is ready；Wherein N, M >=1；
C. film deposition and measurement ALD presoma critical pulse width are carried out using following ALD processing procedure:
It comprises the following processes:
C-a) the ALD deposition of film, a growth cycle includes four pulses:
(1) gas pulses of precursor A are passed through into vacuum reaction chamber；
(2) it is passed through inert gas into vacuum reaction chamber and rinses pulse；
(3) gas pulses of precursor B are passed through into vacuum reaction chamber；
(4) it is passed through inert gas into vacuum reaction chamber and rinses pulse；
Aforementioned four pulse, circulation execute n times；
In step C-a), precursor A suction pulsation, precursor B suction pulsation pass through inert gas and are delivered to vacuum
Reaction chamber, the inert gas refer to: during the ALD deposition of film, not chemically reacting with precursor A, precursor B
Gas.
C-b) utilize the quality incrementss Δ m of QCM real-time measurement film, and by measurement result real-time Transmission to computer or
Other display equipment records quality incrementss Δ m and corresponding precursor A gas pulses width in order；
C-c) precursor A gas pulses width increases Δ t in original value；Then circulation executes step C-a) to C-
B), and so on execute M times；
After M deposition outer circulation, precursor A gas pulses width is by initial default lower limit value tAlowIncrease to pre-
If high limit tAhigh, here, tAhigh-tAlow=M × Δ t；
D. ALD system is closed, film sample is taken out；
It is closed using the function of all previous film quality increment Delta m obtained in step C-b) and precursor A gas pulses width t
System, analysis obtain precursor A critical pulse width, method particularly includes:
Δ m data are normalized, using precursor A gas pulses width t as abscissa, with film quality increment
Δ m is ordinate, in a coordinate system by obtained all previous film quality increment Delta m and corresponding precursor A gas pulses width t
Δ m-t functional image is drawn, one section of horizontal image in functional image in setting relative error limit is selected, it is corresponding horizontal
The initial value of line segment, as precursor A critical pulse width, and indicate that the film of the processing procedure is grown to ALD mode；If Δ m-t
Horizontal line segment is not present in functional image but is increased monotonically, then indicates that the film of the processing procedure is grown to CVD mode.
Preferably, in stepb, cycle-index N is 1-100 in depositing.
Preferably, in stepb, precursor A gas pulses width initial value t0 is set as 0.1s.
Preferably, in stepb, precursor A gas pulses width incremental steps Δ t is 0.1s~1s.
Preferably, analysis obtains precursor A critical pulse width method particularly includes:
Δ m data are normalized, using precursor A gas pulses width t as abscissa, with film quality increment
Δ m is ordinate, in a coordinate system by obtained all previous film quality increment Delta m and corresponding precursor A gas pulses width t
Δ m-t functional image is drawn, one section of horizontal image in functional image in setting relative error limit is selected, it is corresponding horizontal
The initial value of line segment, as precursor A critical pulse width；If horizontal line segment is not present in Δ m-t functional image but list
Length is adjusted, then indicates that the film of processing procedure is grown to CVD mode；
When drawing, free unit (a.u.) technique of painting is can be used in Δ m, i.e., does not mark mass unit, also do not mark the reality of Δ m
Actual value, this is because the definition according to ALD presoma critical pulse width, only ALD presoma critical pulse width shows Δ m
It is and unrelated with the practical absolute value of ordinate Δ m with the horizontal segment of the functional image of t.
When each film quality incrementss Δ m tends to steady state value, this means that precursor gas molecule is in the surface of solids
Coverage rate tend to steady state value (100%), adsorption reaction reaches saturation state.
Beneficial effects of the present invention are as follows:
1, since whole measurement process only needs one film sample of ALD deposition that can measure ALD presoma critical pulse
The cleaning preparation amount of width, substrate material only has 1/the tens of the prior art, and the presoma of required consumption is also very big
It reduces on ground；The ALD equipment duration of runs also shortens to 1/the tens of the prior art simultaneously；
2, due to not needing gradually to deposit large number of film sample as the prior art, specific ALD processing procedure is measured
Presoma critical pulse width, spent time shortens to 1/the tens of the prior art；
3, during the ALD deposition of film, i.e., film quality increment Delta m has been got in real time, in situ with before
The functional relation for driving body A gas pulses width t no longer needs to carry out off-line type test sample film thickness, without using HRTEM high
Resolution transmission electron microscope, elliptic polarization spectrometer, step instrument etc. are come the large number of film sample that measures
Thickness greatly reduces the workload of tester；
4, when measuring ALD presoma critical pulse width, without considering the unit and actual value of Δ m；
5, since whole measurement process is disposably automatically completed in ALD vacuum reaction chamber, the technological parameter one of ALD
Cause property is very perfect, avoids tens of secondary possible techniques of ALD deposition film sample that repeat in the prior art and disperses
Measurement error caused by property.
Detailed description of the invention
Fig. 1 is the Langmuir thermoisopleth of different K values.Wherein ordinate is coverage rate, and abscissa is adsorbate air pressure.
Fig. 2 is the method schematic diagram of quick measurement ALD presoma critical pulse width proposed by the present invention.
Fig. 3 is Bi (thd)3/H2The precursor B i (thd) of the ALD processing procedure of O3Critical pulse width schematic diagram.
Fig. 4 is TMA/H2The precursor B i (thd) of the ALD processing procedure of O3Critical pulse width schematic diagram.
Specific embodiment
The purpose of the present invention, advantage and feature, by by the non-limitative illustration of preferred embodiment below carry out diagram and
It explains.These embodiments are only the prominent examples using technical solution of the present invention, it is all take equivalent replacement or equivalent transformation and
The technical solution of formation, all falls within the scope of protection of present invention.
Embodiment 1
It measures Bi (thd)3/H2The ALD precursor B i (thd) of the ALD processing procedure of O3Critical pulse width:
Prepare sample and sample introduction:
Polished silicon slice substrate material is clean using acetone or washes of absolute alcohol, then use high-purity (99.999%) nitrogen
Air-blowing is dry, is placed into substrate pallet；
Pallet is transmitted by load-lock system into vacuum reaction chamber together with substrate, vacuum pump is opened, to vacuum reaction chamber
It is vacuumized；While vacuumizing, high-purity nitrogen is passed through to vacuum reaction chamber；After a period of time, vacuum reaction
The atmospheric pressure value of chamber can be stablized in certain value；
By the touch screen of equipment, ALD technological parameter is set:
Film deposition temperature is set as 280 DEG C, precursor B i (thd)3Temperature is 178 DEG C, presoma H2O temperature be 18 DEG C,
It is 8s, precursor B i (thd) that nitrogen, which rinses pulse width,3Gas pulses width initial value tAlowFor 0.5s, presoma H2O gas
Pulse width is 0.2s, precursor B i (thd)3Gas pulses width incremental steps Δ t is 0.5s, cycle-index N is in deposition
100, deposition outer circulation number M is 30, measurement relative error is limited to 5%, is faced for the ALD deposition and measurement ALD presoma of film
Boundary's pulse width is ready；
Film deposition and measurement ALD presoma critical pulse width are carried out using following ALD processing procedure:
It comprises the following processes:
A) ALD deposition of film, a growth cycle includes four pulses:
(1) precursor B i (thd) is passed through into vacuum reaction chamber3Gas pulses；
(2) it is passed through nitrogen into vacuum reaction chamber and rinses pulse；
(3) presoma H is passed through into vacuum reaction chamber2The gas pulses of O；
(4) it is passed through nitrogen into vacuum reaction chamber and rinses pulse；
Aforementioned four pulse, circulation execute 100 times；
In step a), precursor B i (thd)3Suction pulsation, presoma H2O suction pulsation passes through nitrogen and is delivered to very
Empty reaction chamber.
B) the quality incrementss Δ m of QCM real-time measurement film is utilized, and by measurement result real-time Transmission to Computer display
Device records quality incrementss Δ m and corresponding precursor B i (thd) in order3Gas pulses width；
C) precursor B i (thd)3Gas pulses width increases 0.5s in original value；Then circulation executes step a) extremely
B), and so on execute 30 times；
ALD system is closed, film sample is taken out；
Utilize all previous film quality increment Delta m obtained in step b) and precursor B i (thd)3Gas pulses width t's
Functional relation, Δ m-t functional image is drawn by computer program over the display, and analysis obtains precursor B i (thd)3It is critical
Pulse width is 6.5s, as shown in Fig. 3.
Embodiment 2
To measure TMA/H2(TMA is the contracting of trimethyl aluminium for the presoma TMA critical pulse width of the ALD processing procedure of O
Write):
Operating procedure is substantially the same manner as Example 1, the difference is that:
Set ALD technological parameter:
Set film deposition temperature as 300 DEG C, presoma TMA temperature be 18 DEG C, presoma H2O temperature is 18 DEG C, nitrogen
Flushing pulse width is 8s, presoma TMA gas pulses width initial value tAlowFor 0.1s, presoma H2O gas pulses width is
0.2s, presoma TMA gas pulses width incremental steps Δ t are 1s, cycle-index N is 10, deposits outer circulation number M in deposition
3% is limited to for 10, measurement relative error；
Using the functional relation of obtained all previous film quality increment Delta m and presoma TMA gas pulses width t, lead to
It crosses computer program and draws Δ m-t functional image over the display, it is 0.1s that analysis, which obtains presoma TMA critical pulse width,
As shown in Fig. 4.In this embodiment, the corresponding film quality of most short and longest TMA gas pulses width (0.1s and 1s) increases
Δ m percentage difference is measured less than 3%.This means that presoma TMA critical pulse width is 0.1s.Due to the machine of electromagnetic valve
The limitation of tool response characteristic, 0.1s has been the minimum value of set pulse width.
Still there are many embodiment, all technical sides formed using equivalents or equivalent transformation by the present invention
Case is within the scope of the present invention.
Claims (9)
1. a kind of method of quickly measurement sequential keyboard encoder ALD presoma critical pulse width, it is characterised in that:
The ALD presoma critical pulse width is related to the parameter of used presoma, ALD equipment；
In sequential keyboard encoder ALD processing procedure single growth circulation in include a precursor A gas pulses, a precursor B gas pulses,
Two inert purge gas pulses；In the ALD equipment used in deposition film sample, obtained configured with being used to monitor ALD deposition in real time
The QCM of the quality incrementss Δ m of the film arrived；
During measuring ALD presoma critical pulse width, inert gas rinse pulse width, inert gas flow velocity,
The gas pulses width of matched another precursor B, the vessel temp of each presoma, ALD deposition temperature T, that is, vacuum reaction chamber
Temperature remains unchanged, and precursor A gas pulses width t from be short to length be gradually increased, obtained film is measured by QCM
Quality knots modification Δ m in the specified deposition cycle of each precursor A gas pulses width t, finally obtains each film
The functional relation of quality incrementss Δ m and precursor gas pulse width t, the functional relation for analyzing obtained Δ m and t are come really
The ALD precursor A critical pulse width of fixed used sequential keyboard encoder ALD processing procedure；
The method of the quick measurement sequential keyboard encoder ALD presoma critical pulse width deposits an independent film by ALD processing procedure
Sample is the presoma critical pulse width that can determine used sequential keyboard encoder ALD processing procedure；In the method, ALD precursor gas
Body pulse width t can by controlling change；
This method specifically comprises the following steps:
A. sample and sample introduction are prepared；
B. ALD technological parameter is set:
Set precursor A gas pulses width initial value tAlow, precursor A gas pulses width incremental steps Δ t, follow in deposition
Ring times N, deposition outer circulation number M, measurement relative error limit are the ALD deposition and measurement ALD presoma critical pulse of film
Width is ready；Wherein N, M >=1；
C. film deposition and measurement ALD presoma critical pulse width are carried out using following ALD processing procedure:
It comprises the following processes:
C-a) the ALD deposition of film, a growth cycle includes four pulses:
(1) gas pulses of precursor A are passed through into vacuum reaction chamber；
(2) it is passed through inert gas into vacuum reaction chamber and rinses pulse；
(3) gas pulses of precursor B are passed through into vacuum reaction chamber；
(4) it is passed through inert gas into vacuum reaction chamber and rinses pulse；
Aforementioned four pulse, circulation execute n times；
In step C-a), precursor A suction pulsation, precursor B suction pulsation pass through inert gas and are delivered to vacuum reaction
Chamber, the inert gas refer to: during the ALD deposition of film, the gas that is not chemically reacted with precursor A, precursor B
Body；
C-b) utilize QCM real-time measurement film quality incrementss Δ m, and by measurement result real-time Transmission to computer or other
It shows equipment, records quality incrementss Δ m and corresponding precursor A gas pulses width in order；
C-c) precursor A gas pulses width increases Δ t in original value；Then circulation executes step C-a) to C-b), according to
It is secondary to analogize execution M times；
After M deposition outer circulation, precursor A gas pulses width is by initial default lower limit value tAlowIncrease to default height
Limit tAhigh, here, tAhigh-tAlow=M×Δt；
D. ALD system is closed, film sample is taken out；
Using the functional relation of all previous film quality increment Delta m obtained in step C-b) and precursor A gas pulses width t,
Analysis obtains precursor A critical pulse width.
2. the method as described in claim 1, it is characterised in that:
Δ m-t functional image is drawn on graph paper by hand by operator, or is automatically drawn by computer program；It is drawing
When, Δ m uses free unit (a.u.) technique of painting.
3. the method as described in claim 1, it is characterised in that:
In stepb, cycle-index N is 1-100 in depositing.
4. such as the described in any item methods of claim 1, it is characterised in that:
In stepb, precursor A gas pulses width initial value tAlowIt is set as 0.1s.
5. method according to any of claims 1-4, it is characterised in that:
In stepb, precursor A gas pulses width incremental steps Δ t is 0.1s~1s.
6. method according to any of claims 1-4, it is characterised in that:
Analysis obtains precursor A critical pulse width method particularly includes:
Δ m data are normalized, using precursor A gas pulses width t as abscissa, with film quality increment Delta m
For ordinate, obtained all previous film quality increment Delta m and corresponding precursor A gas pulses width t are drawn in a coordinate system
Δ m-t functional image out selects one section of horizontal image in functional image in setting relative error limit, corresponding horizontal line
The initial value of section, as precursor A critical pulse width, and indicate that the film of the processing procedure is grown to ALD mode；If Δ m-t letter
Horizontal line segment is not present in number image but is increased monotonically, then indicates that the film of the processing procedure is grown to CVD mode.
7. method according to any of claims 1-4, it is characterised in that:
In stepb, relative error limit is set as 2%~5%.
8. method according to any of claims 1-4, it is characterised in that:
The step A concrete operations are as follows: the substrate material of cleaning is dried up with inert gas, is placed into substrate pallet；
Pallet moves into vacuum reaction chamber together with substrate, opens vacuum pump, vacuumizes to vacuum reaction chamber.
9. method according to any of claims 1-4, it is characterised in that:
In the step B, further includes: setting film deposition temperature T, precursor A temperature, precursor B temperature, inert gas rinse
Pulse width, precursor B gas pulses width.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711222641.1A CN107974667B (en) | 2017-11-28 | 2017-11-28 | A kind of method of quick measurement sequential keyboard encoder ALD presoma critical pulse width |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711222641.1A CN107974667B (en) | 2017-11-28 | 2017-11-28 | A kind of method of quick measurement sequential keyboard encoder ALD presoma critical pulse width |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107974667A CN107974667A (en) | 2018-05-01 |
| CN107974667B true CN107974667B (en) | 2019-08-16 |
Family
ID=62008442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711222641.1A Active CN107974667B (en) | 2017-11-28 | 2017-11-28 | A kind of method of quick measurement sequential keyboard encoder ALD presoma critical pulse width |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107974667B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101116B (en) * | 2018-10-25 | 2023-08-18 | 北京北方华创微电子装备有限公司 | Process gas delivery device, atomic layer deposition method and deposition equipment |
| CN117265510B (en) * | 2023-11-24 | 2024-02-27 | 上海星原驰半导体有限公司 | Atomic layer deposition method and atomic layer deposition system |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004031453B4 (en) * | 2004-06-29 | 2009-01-29 | Qimonda Ag | Method for producing a dielectric and semiconductor structure |
| CN102337523A (en) * | 2011-10-13 | 2012-02-01 | 姜谦 | Selective atomic layer deposition film formation method |
| CN103451623B (en) * | 2013-08-20 | 2015-08-26 | 华中科技大学 | A kind of Atomic layer deposition method of Coated powder and device |
| JP6562629B2 (en) * | 2013-12-30 | 2019-08-21 | ラム リサーチ コーポレーションＬａｍ Ｒｅｓｅａｒｃｈ Ｃｏｒｐｏｒａｔｉｏｎ | Plasma atomic layer deposition with pulsed plasma exposure |
-
2017
- 2017-11-28 CN CN201711222641.1A patent/CN107974667B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107974667A (en) | 2018-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101111628B (en) | Method and apparatus for monolayer deposition (mld) | |
| CN107974667B (en) | A kind of method of quick measurement sequential keyboard encoder ALD presoma critical pulse width | |
| JP4994245B2 (en) | Monolayer deposition method | |
| US20160168710A1 (en) | Gas Injection System For Chemical Vapor Deposition Using Sequenced Valves | |
| US7881886B1 (en) | Methods for performing transient flow prediction and verification using discharge coefficients | |
| US10502651B2 (en) | Creating a mini environment for gas analysis | |
| US8671733B2 (en) | Calibration procedure considering gas solubility | |
| CN105506581B (en) | A kind of implementation method preparing film using technique for atomic layer deposition | |
| CN106093134B (en) | The compensation method of metal oxide sensor array response drift | |
| CN111249932A (en) | Gas dynamic dilution and distribution method and device | |
| CN107974666B (en) | A kind of method of the ALD-window of quick measurement sequential keyboard encoder ALD processing procedure | |
| US20090152242A1 (en) | Plasma treatment apparatus and plasma treatment method | |
| JP5954739B2 (en) | Method and apparatus for on-site analysis of gases in electronic device manufacturing systems | |
| US7540918B2 (en) | Atomic layer deposition equipment and method | |
| Varnakov et al. | Automation of technological equipment for obtaining multilayer structures in an ultrahigh vacuum | |
| CN109659254A (en) | The method that handled object is handled | |
| US20140014681A1 (en) | Calibration of a Chemical Dispense System | |
| CN212083170U (en) | Flue gas partition measuring system capable of unifying dilution ratio | |
| JPH0955185A (en) | Mass filter type gas analyzer with calibration gas system and its operating method | |
| KR20100040439A (en) | Measuring method of thin film and measuring apparatus of thin film | |
| CN108231518A (en) | For the virtual-sensor of chamber clean terminal | |
| KR101323885B1 (en) | A precursor vapor pressure measuring device for precursor | |
| US6881259B1 (en) | In-situ monitoring and control of germanium profile in silicon-germanium alloy films and temperature monitoring during deposition of silicon films | |
| KR20160114265A (en) | Gas component quantitative analysis apparatus with automatic feed control function of gas in multiple sample gas bags | |
| Shah et al. | Installation of an FS-1 in situ Ellipsometer on an Atomic Layer Deposition (ALD) System. Part 1. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230817 Address after: 226000 Jiangsu city of Nantong province sik Road No. 9 Patentee after: Nantong University Technology Transfer Center Co.,Ltd. Address before: 226019 Jiangsu Province, Nantong City Chongchuan District sik Road No. 9 Patentee before: NANTONG University |
|
| TR01 | Transfer of patent right | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180501 Assignee: Nantong Fujun Electronic Technology Co.,Ltd. Assignor: Nantong University Technology Transfer Center Co.,Ltd. Contract record no.: X2023980049369 Denomination of invention: A Rapid Method for Determining the Critical Pulse Width of Sequential ALD Precursors Granted publication date: 20190816 License type: Common License Record date: 20231203 |
|
| EE01 | Entry into force of recordation of patent licensing contract |