Adv Materials Inter - 2023 - Chen - Wafer‐Scale Highly Uniform Surface Functionalization from Vapor Phase and Applications

Research Article

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Wafer-Scale, Highly Uniform Surface Functionalization from

Vapor Phase and Applications to Organic Transistors
Ming Chen, Jie Li, Yingzhe Piao, Wanli Yang, Chun Li, Yi Wan, Yanhao Yu, Lain-Jong Li,
Xugang Guo, and Xing Cheng*
Particularly, it is believed that surface

The surface functionalization by self-assembled monolayers (SAMs) favors functionalization could alter the surface
well-packed organic semiconductor growth and reduces interfacial traps, energy and reduce the interfacial trap
which assists in developing high-performance organic thin-film transistors states and hence is broadly integrated into
the fabrications and optimizations of the
(OTFTs). Herein, the conventional SAM growth from the vapor phase is
organic thin-film transistors (OTFTs). For
ameliorated and systematically studied. With 1H,1H,2H,2H-Perfluorodecyl- example, octadecyltrichlorosilane (OTS)
trichlorosilane as an example, it is found that deposition temperature of no with low surface energy is employed for
less than 120 °C and deposition pressure of up to 0.02 bar is preferred for enabling well-oriented organic semicon-
SAM deposition without morphological defects. The optimized SAMs are ultr- ductor thin films.[3–7] The phenyltrichlo-
asmooth with a surface roughness of 0.09 nm and can be escalated to wafer rosilane (PTS) is frequently utilized for
the solution-processed single-crystalline
scale. It is verified that the growth condition is universal for other trichlorosi-
organic layer growth owing to the higher
lane species. Finally, it is shown that the OTFTs with defect-free SAMs can surface energy over the common organic
achieve an average mobility of 1.79 cm2 V−1 s−1 using dinaphtho(2,3-b:2′,3′-f ) semiconductor solvents (heptane, toluene,
thieno(3,2-b)thiophene as the active layer, which is 2.06 times to the devices m-xylene, etc.) and ensures a good wet-
with defective SAMs and paces up the large-area and high-performance tability.[8–11] The highly ordered active
layer and the high-quality organic semi-
organic electronics.
conductor-dielectric interface with negli-
gible trap states are the essential building
blocks to enable high-performance OTFTs
1. Introduction and OTFT-based applications, which cover over a wide range of
areas, including the logic circuits,[6,12–14] sensors,[15–17] memory
The surface functionalization by self-assembled monolayers devices and display drivers.[5,18,19] Moreover, it is fascinating that
(SAMs) provides fine control over superficial/interfacial proper- surface functionalization can effectively modulate the channel
ties and enables a wide range of applications, including nano- carrier density and provide fine control over the threshold
imprint technology,[1] microelectromechanical systems, etc.[2] voltage,[20,21] which necessitates high-quality surface treatment.
However, due to the complexity of the fabrication process, the
M. Chen, J. Li, Y. Piao, W. Yang, C. Li, Y. Yu, X. Guo, X. Cheng morphological defects generated during the growth of SAMs
Department of Materials Science and Engineering immensely affect the quality of the surface functionalization
Southern University of Science and Technology and the OTFT performance. Accordingly, surface functionaliza-
Shenzhen, Guangdong 518055, China
E-mail: [email protected] tion with negligible morphological defects is highly desired.
M. Chen, J. Li, Y. Piao, X. Cheng The surface functionalizing SAMs are typically grown from
Shenzhen Key Laboratory for Nanoimprint Technology either solution or vapor phase.[22] In the liquid phase method,
Southern University of Science and Technology the substrates are generally immersed into the SAM solutions
Shenzhen, Guangdong 518055, China for several hours and even up to tens of hours.[4–6,8,10] Although
Y. Wan, L.-J. Li the quality of the surface functionalization based on the immer-
Department of Mechanical Engineering
The University of Hong Kong
sion method could be improved by optimizing the deposition
Pokfulam Road, Hong Kong 999077, China temperature and the solvent,[23,24] the long processing time
allows the organosilane molecules to form aggregations, and
The ORCID identification number(s) for the author(s) of this article the subsequent deposition on the substrate surface leads to the
can be found under https://doi.org/10.1002/admi.202202453. irregular defects on the substrate surface. The phenomena have
© 2023 The Authors. Advanced Materials Interfaces published by been observed and reported previously.[6,25,26] As the solvents-
Wiley-VCH GmbH. This is an open access article under the terms of the free approach, the surface functionalization by vapor phase
Creative Commons Attribution License, which permits use, distribution avoids the issues associated with the solution method,[27] such
and reproduction in any medium, provided the original work is properly
cited. as effects originated from viscosity and polarity of the solvent,[24]
the diffusion-limited transport of the organosilane molecules
DOI: 10.1002/admi.202202453 onto the substrate, the uncertain reaction of organosilanes in
Adv. Mater. Interfaces 2023, 10, 2202453 2202453 (1 of 8) © 2023 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH
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www.advancedsciencenews.com
the solvents, etc.[28]

In the vapor phase approach, the silane mobility (µ) of 1.79 cm2 V−1 s−1,
which is 2.06 times compared
liquids evaporate and the molecules are deposited on the sub- to the devices fabricated from defective SAMs. This study pro-
strates to form the SAMs. Normally, control over temperature vides a general approach for surface functionalization without
and vacuum degree is required to accelerate the silane vaporiza- morphological defects to improve charge carrier mobility. In
tion. One more distinct feature of the vapor phase is the better addition, the wafer-scale depositions have enabled large-area
reproducibility and scalability, compatible with the manufac- device fabrication and foreshadowed the high integration and
ture of large-area electronics,[27,29] which hence meets the com- mass production of organic electronics. Not only limited to
mercialization requirement. Although many efforts have been OTFTs, but the defect-free SAMs are also favorable for diverse
devoted to SAM deposition, how to provide a favorable growth applications regarding surface functionalization.
environment and optimize the processing conditions to elimi-
nate the morphological defects and ultimately reach wafer-scale
functionalization remains unclear. 2. Results and Discussion
The conventional vapor phase approach is usually suffering
from contamination from the reaction vessel. We have found The silanes utilized are identical in the -SiCl3 head to be spe-
that the employment of an extra glass petri dish covered with cifically anchored onto the silicon (Si) substrate but differ in the
aluminum (Al) foil could effectively reduce the contamina- functional groups. Figure 1a depicts the molecular structures
tion from the vessel and confine the vapor in a localized area, of PTS, FDTS, and OTS with distinct terminal groups. Herein,
eventually attaining high-quality SAMs without morphological the frequently used FDTS with highly nonpolar characteristics
defects. Herein, the vapor phase growing approach is system- is employed for the growth study.[29–31] As would be discussed
atically studied with 1H,1H,2H,2H-perfluorodecyltrichlorosi- in the following, the highly dispersive feature allows the evalu-
lane (FDTS) for high-quality surface functionalization. The ation of the saturated vapor pressure and favors the deposition
processing parameters are adopted based on the derived vapor parameter determination. As shown in Figure 1b, surface func-
pressure of the FDTS and ameliorated by varying the pro- tionalization is accomplished by allowing an aluminum foil-
cessing parameters, including the deposition temperature (TD) covered glass petri dish standing in the vessel, which contains
and the deposition pressure (PD). After optimization, morpho- both the silane solution and the Si substrates. To facilitate the
logical defects-free and up-to-wafer-scale SAMs are attained FDTS vaporization, the vessel is heated and pumped down to a
with a surface roughness (Rq) of 0.09 nm. It was found that high vacuum degree (0.02 bar). As presented in Figure 1c, the
this protocol is universal when applied to other trichlorosi- FDTS vapor diffuses and is adsorbed onto the substrate to form
lane materials, that is, OTS and PTS. The defect-free surface the self-assembled monolayer by covalent bonding (the inset in
functionalization of OTS is then employed in the organic thin- Figure 1c).
film transistors for achieving a high-quality organic semicon- The evaporation behavior of FDTS is correlated to the
ductor-dielectric interface with the organic semiconductor of vapor pressure (p), which relies on both the deposition tem-
dinaphtho(2,3-b:2′,3′-f)thieno(3,2-b)thiophene (DNTT). The perature, and the boiling points (TB) of the silanes. As shown
transistors with defect-free SAMs show an average carrier in Equation (1), the dependence of vapor pressure on the
Figure 1. The deposition of silanes from the vapor phase. a) Molecular structure of silanes utilized in the study. Apart from the SiCl3 head, the
terminals of X are the functional groups. Typically, the molecules represent PTS (pink), FDTS (blue), and OTS (red) by varying the functional groups.
b) Schematic diagram of the surface functionalization with FDTS. A glass petri dish containing both FDTS and oxygen plasma-treated Si is placed
inside the reaction vessel. The Al foil covering the glass petri dish is omitted for better clarification. c) Surface functionalization process inside the
glass petri dish. As the precursor evaporates under environments of high temperature and high vacuum degree, the FDTS molecules are deposited on
the substrate. The inset shows the schematic illustration of the molecules packing of FDTS on the substrate as depicted by the rectangle in black dash
line. d) Vapor pressure of FDTS with respect to the temperature by plugging the parameters into the equation as shown in the plot. The two dash lines
represent the standard atmospheric pressure (blue dash line) and 0.02 bar (red dash line), respectively.
temperature (T) is well described by the Clausius-Clapeyron morphology and becomes dense for TD = 80 °C, while a flat
equation:[32,33] FDTS surface appears at high TD (120 and 160 °C). As depicted
by the profile along the white dash line, the height of the FDTS
p  L  1 1 island is ≈2.6 nm, identical to the bilayer thickness. The bilayer
ln  2  = − H  −  (1)
 p1  R  T2 T1  phenomenon has been observed and reported previously, which
could attribute to the formation and rupture of the inverse
where the subscripts of 1 and 2 denote different states, LH is the vesicles.[26] On the other hand, deposited from low tempera-
latent heat or enthalpy of vaporization (ΔHvap) and R is the ideal tures, the FDTS molecules interact with each other and the
gas constant (8.314 J mol−1 K−1). As state 1 reaches the equilib- substrate primarily by hydrogen bonding in between SiOH
rium evaporation state, the p1 and T1 could be replaced by the and are prone to move under thermal processing. The high TD
standard atmospheric pressure (P) and boiling point, namely is required to eliminate the island structures and the FDTS
p1 = P and T1 = TB. The Equation (1) is then reduced to: film is condensed and locked to the substrate via cross-linked
SiOSi bonding.[26]
p L 1 1
ln   = − H  −  (2) To explore the effect of deposition pressure on the FDTS
P R  T TB  morphology, four distinct deposition pressures are applied
Here we have removed the subscript of 2 and p and T repre- at a constant high temperature of 120 °C. Figure 2i–l shows
sent pressure and temperature at arbitrary states. In the equi- the AFM images of the FDTS-treated Si substrates under dif-
librium state, the Gibbs free energy (ΔG) is zero and that is: ferent pressures. Although the FDTS is successfully deposited
as verified by the water contact angle (Figure 2m–p), the sur-
∆G = ∆H vap − TB ∆Svap = 0 (3) face morphology differs greatly. As the degree of vacuum level
In Equation (3), ΔSvap is entropy at an equilibrium state. The escalates, the amount of the aggregates decreases gradually and
LH is then expressed by: ultimately vanishes when the PD reaches 0.02 bar, implying that
the high degree of vacuum level is imperative for the elimina-
LH = ∆H vap = TB ∆Svap (4)
tion of the aggregation defects. The height of the aggregates
The vapor pressure in exponential form is obtained by incor- exceeds 10 nm as measured by the cross-section profile in the
porating Equations (2),(4): inset of Figure 2k, which differs from the bilayer defects. The
LH  1 1  ∆Svap  TB 
contact angles do not change significantly and the dependence
 − T   1−  (5)
p = P e R  TB = Pe R  T  of contact angles on the processing variables and defects is not
investigated here. The result here reveals that the contact angle
Similar expressions have been derived elsewhere.[34] There- measurements could not reflect the microscopic feature of sur-
after, Trouton’s law (i.e., ΔSvap ≈ 10.5R) is applied for the esti- face modification. Normally, the deposition of SAMs involves
mation of the heat of evaporation at one atmospheric pressure, hydrolysis and condensation steps.[26,36] The hydrolysis is
which generally agrees well with no polar compound.[35] The essential for the deposition of SAMs since the silanetriols
surface energy of FDTS is a dispersive term dominated with have a strong affinity to the hydroxyl substrate via hydrogen
low polar components, validating the applicability of Trouton’s bonding.[26,37,38] In hydrolysis, the SiCl3 components of
law. By plugging the TB information of FDTS (Table S1, Sup- FDTS molecules interact with the water to form the SiOH
porting Information) into Equation (5), the vapor pressure is groups. The molecules with hydroxyl groups then form the
outlined in Figure 1d. It can be seen that in the temperature SiOSi bonds in both the lateral direction to each other
range from 30 to 200 °C, the vapor pressure of FDTS is far and the vertical direction to the Si substrate. Given the observed
below the standard atmospheric pressure (blue dash line), sug- inverse relationship between the number of irregular spots and
gesting negligible evaporation. To facilitate the vaporization, the vacuum degree, the aggregation is attributed to the high
the deposition pressure is greatly reduced to 0.02 bar (red dash amount of water and enhanced hydrolysis associated with the
line), which is comparable to the saturated vapor pressure. deposition pressure.[24] When PD is high, namely low vacuum
The influence of the deposition temperature is investigated degree, plenty of water molecules remain in the vessel and
while maintaining the deposition pressure at 0.02 bar. Prior strengthen the hydrolysis reaction to generate the aggregates,
to the surface treatment, the morphology and surface energy which then fall on the substrate. The growth study of FDTS
of the original Si substrate are characterized. As shown in suggests that particular attention to the deposition temperature
Figure S1 (Supporting Information), the surface scanned by the (TD ≥ 120 °C) and pressure (PD ≤ 0.02 bar) should be paid for
Atomic Force Microscope (AFM) is highly uniform with a low spot-free surface functionalization.
surface roughness of 0.09 nm and provides a superb platform As a significant property of surface functionalization, the sur-
for SAM growth. In addition, the surface energy of the unfunc- face energy of the FDTS films on Si substrate without morpho-
tionalized Si substrate is found to be 49.78 mJ m−2 (Figure S2, logical defects is determined by measuring the contact angles.
Supporting Information). Figure 2a–d depicts the surface Two standard liquids are employed, as shown in Figure 3a,b.
morphology of FDTS film-covered Si substrate deposited The contact angles are 109.07 ± 2.08° and 97.75 ± 1.63° for
from four different TD, including 40, 80, 120, and 160 °C. The water and diiodomethane, respectively. Both the contact
water contact angles are measured as shown in Figure 2e–h. values indicate the hydrophobic feature. The surface energy of
All the contact angle values reveal a hydrophobic feature, indi- 10.33 mJ m−2 including the dispersive term of 7.58 mJ m−2 and
cating the successful deposition of FDTS. However, under the the polar term of 2.75 mJ m−2 is obtained for FDTS on Si sub-
deposition temperature of 40 °C, the FDTS features island strate based on the Owen–Wendt–Rabel–Kaelble model. It is
Figure 2. The surface functionalization study by varying the deposition parameters. a–d) Morphology of the FDTS films as a function of the TD of a) 40,
b) 80, c) 120, and d) 160 °C in an increasing succession (green arrow) under a constant PD of 0.02 bar. In addition, the corresponding contact angles
are measured, as shown in (e–h). The inset in (a) shows the height profile as indicated by the white dash line and the contact angle values are labeled.
i–l) AFM image of FDTS growth as a function of the pressures, including i) 0.2, j) 0.1, k) 0.05, and l) 0.02 bar. The surface roughness of (l) is 0.09 nm.
In (k), the inset depicts the outline along the white dash line. Herein, the TD is maintained at 120 °C. The water contact angles are illustrated in (m–p).
In the bottom of the figures, the green arrow represents the vacuum degree elevation sequence.
worth noting that the polar component is ≈3 mJ m−2, indicating than pure Si substrates, the functionalization process is usually
the weak polar characteristic and validating the utilization of applied to the SiO2 surface to meliorate the interface proper-
Trouton’s law as discussed in the previous vapor pressure deri- ties between the organic semiconductor and dielectric layer. As
vation.[35] The deposition of the FDTS is further examined by such, we have performed the SAM growth on the Si substrate
X-ray photoelectron spectroscopy (XPS), together with the bare with 300 nm thermally grown SiO2. The Si/SiO2 is subjected
Si substrate. Three elements are measured, including C, F, and to oxygen plasma treatment and functionalization with FDTS
Cl. Other than the CC peak located at 284.8 eV, the FDTS- (Figure S3, Supporting Information). At each stage, the sur-
modified Si substrate exhibits two extra C peaks at 290.9 and face morphology characterizations manifest an almost identical
293.3 eV, compared to the untreated Si substrate (Figure 3c). surface roughness, imparting the perfect SAM deposition. More-
These two peaks are designated to the moieties of CF2 and CF3. over, the low surface energy of 10.69 mJ m−2 confirms the suc-
In the meantime, an obvious F peak is observed, indicating the cessful FDTS deposition on the SiO2 surface as well (Figure S4,
successful deposition of FDTS (Figure 3d). No Cl signals could Supporting Information). Furthermore, the large area scalability
be seen for both the FDTS-treated or non-treated Si substrates, is accomplished with the 4-inch wafer as the functionalized
divulging the hydrolysis reaction of FDTS during the surface substrate. All the AFM images scanned at different locations
functionalization process. The thickness of the defect-free reveal even morphology, indicating the good scalability of the
FDTS is measured to be 1.31 nm by ellipsometer, which agrees current deposition process (Figure 3f). The high-quality surface
well with the monolayer of the reported values.[26,39,40] Other functionalization should lead to the high performance, stability,
Figure 3. Characterization of the wafer-scale defect-free FDTS modified Si substrates. a,b) Contact angle measurement from a) water and
b) diiodomethane for the surface energy determination. From these contact angle values shown, the surface energy is calculated to be 10.33 mJ m−2.
The dispersive term is 7.58 mJ m−2 and the polar term is 2.75 mJ m−2. c–e) XPS characterization of the FDTS treated Si (red lines), together with the
pure Si substrate (black lines) regarding the elements of c) C, d) F and e) Cl. In (c), the chemical bonding of CC, CF2, and CF3 are labeled. f) AFM
characterization of the wafer-scale FDTS growth. Different areas from 1 to 5 show uniform and smooth surface morphology.
and well repeatability of the organic electronic devices, and of OTS on the Si substrate. Under the deposition temperature
wafer-scale scalability sheds the light on the mass production of of 120 °C and the deposition pressure of 0.2 bar, irregular spots
the large-area, highly integrated electronics. are dispersive on the surface (Figure 4b). As discussed previ-
The generality is verified by applying the growth conditions ously, the low degree of vacuum allows a large amount of mois-
to the other two frequently used SAMs, including both OTS ture residing in the vessel and enhances the hydrolysis to form
and PTS (Figure 4). Figure 4a depicts the molecular structure large aggregates. The quality of the OTS is greatly improved
Figure 4. The generality of the processing conditions to frequently used trichlorosilanes. a) Molecular packing of OTS on Si substrate. The elements
are labeled. b,c) AFM images of the OTS (b) with aggregates (processed at 120 °C and 0.2 bar) and (c) without aggregates (processed at 160 °C and
0.02 bar). d) Illustration of molecular packing of PTS on the Si substrate. e,f) Surface morphology of PTS SAM characterized by AFM, which is depos-
ited at e) 120 °C and 0.2 bar and f) 160 °C and 0.02 bar. g) Surface energies of the pure Si substrate and the trichlorosilane treated substrates used in
the current investigation.
by reducing the PD to 0.02 bar. Due to the high boiling point similar for OTS and PTS with only a C peak detected, whereas dif-
of OTS (Table S1, Supporting Information), herein, the pro- ferent results are found for the surface energy. From the contact
cessing temperature is increased to 160 °C to assist the evapora- angle values using water and diiodomethane, the surface ener-
tion. Figure 4c presents the surface morphology of OTS after gies are assessed, showing the values of 24.49 and 40.7 mJ m−2
the optimizations of the deposition parameters. Similarly, a for OTS and PTS, respectively (Figure 4g). The defect-free func-
high-quality PTS (Figure 4d) is obtained by optimizing the tionalization by FDTS, OTS, and PTS shows a wide range of
variables. The functionalization at a low degree of vacuum surface energy from ≈10 to 40 mJ m−2, hence providing an out-
(0.2 bar) displays scattered dots (Figure 4e), while defect-free standing approach for effective surface modification.
PTS SAM is realized with the increased degree vacuum of To explore the effect of high-quality interface on the
0.02 bar (Figure 4f). The high-quality OTS and PTS SAMs are OTFT performance, the SAMs were incorporated into the
characterized based on the surface energy and the XPS analysis OTFT devices using DNTT as the semiconductor material
(Figures S5, S6, Supporting Information). The XPS results are (Figure 5a,b). The bottom-gate/top-contact (BG/TC) architecture
Figure 5. The application of defect-free OTS to the organic thin-film transistors. a) Schematic diagram of the staggered OTFT device with the semi-
conducting layer of DNTT. b) Molecular structure of DNTT. c) Carrier mobilities by optimizing the organic semiconductor-dielectric interface. Inset
shows the AFM images of the interfaces, including (i) non-treated SiO2, (ii) defective OTS treatment, and (iii) defect-free OTS treatment with a surface
roughness of 0.2, 2.1, and 0.19 nm, respectively. d–f) Typical transfer curves from the device fabricated with (d) non-treated SiO2, (e) defective OTS,
and (f) defect-free OTS. Apart from the logarithm scale (black curves), the square root of the IDS is plotted for carrier mobility extraction. The drain to
source voltage (VDS) used here is −80 V. g–i) Corresponding output curves to (d–f). The gate voltage (VG) is swept from 0 to −80 V with a step of −20 V.
is constructed by thermally evaporating a 40 nm organic semi- the DNTT active layer, which is 2.06 times compared to that
conductor layer and 30 nm gold (Au) source/drain electrodes achieved in the devices with defective OTS treatment. The cur-
(Figure 5a). As defined by the shadow mask, the conduction rent study offers a universal guideline for high-quality surface
channel has a width (W) of 249 µm and a length (L) of 218 µm, treatment, which favors the implementation of high-mobility
yielding a W/L ratio of ≈1.14. Three surface treatments are OTFTs. In addition, the wafer-scale depositions have foreshad-
utilized prior to the active layer deposition, including i) non- owed the large-area fabrication of organic electronic devices.
treated, ii) defective OTS and iii) defect-free OTS and their
surface morphologies are presented (inset of Figure 5c) with
an Rq of 0.2, 2.1, and 0.19 nm, respectively. To eliminate the 4. Experimental Section
fringe current, the active layers were scratched along the Au
electrodes.[41] The electrical characterizations of the OTFTs were Surface Functionalization and Characterization: The Si substrates
without further cleaning were treated with oxygen plasma at 150 W for
then performed and the carrier mobilities were extracted, as
5 min (PDC-MG). After the hydrophilic treatment, both the substrate
shown in Figure 5c. With the functionalization of the defective and 100 µL FDTS (Aladdin) liquid were placed into an aluminum foil-
OTS, the average hole mobility (µh) is drastically increased from covered glass petri dish, which was then put into the vessel with the
0.21 ± 0.02 cm2 V−1 s−1 to 0.87 ± 0.06 cm2 V−1 s−1, albeit the sur- temperature of TD immediately. The glass petri dish was utilized to
face is quite coarse. The mobility is further improved when the reduce the contamination from the reaction vessel. Then, the vessel was
OTFTs are fabricated with the defect-free OTS SAM, yielding pumped down to PD and maintains the TD and PD for 10 min. After the
an average µh of 1.79 ± 0.12 cm2 V−1 s−1, which shows 2.06 times reaction, the residual FDTS vapor was pumped out and the samples
were taken out after the inflation. Different parameters were selected for
compared to the µh of the defective OTS-based devices. As the the growth investigation, including i) TD = 40, 80, 120, and 160 °C when
conduction channel is near the DNTT/OTS interface, the defect- PD = 0.02 bar and ii) PD = 0.2, 0.1, 0.05, and 0.02 bar when TD = 120 °C.
free OTS favors the carrier flow, leading to higher current and The thickness of FDTS was measured by an ellipsometer (TF-UVISEL).
hole mobility. Basically, the hole mobility is independent of the The refractive index of FDTS was 1.35 and the Cauchy dispersion model
silane thickness provided the surface roughness maintains the (A = 1.35, B = 0, C = 0) was utilized for the thickness determination
same. The typical transfer and output curves are illustrated in for FDTS on the Si/SiO2 (2.1 nm)/FDTS layer structure.[30,43] Besides,
Si with 300 nm oxide was functionalized with FDTS. The application
Figure 5d–i. A distinctive difference is that the device without
to OTS (J&K Scientific) and PTS (J&K Scientific) was carried out
any treatment shows much low current values, which is attrib- with100 µL of the liquids under two disparate conditions, comprising
uted to the substantial surface traps, such as OH groups pre- i) TD = 120 °C and PD = 0.2 bar and ii) TD = 160 °C and PD = 0.02 bar.
sented in the non-treated SiO2 surface.[6,42] Such interface effect Detailed determination of the processing parameters was discussed in
has also been observed in the high-mobility organic semicon- the main text. The current study was conducted under relative humidity
ductor of 2,9-didecyldinaphtho(2,3-b:2′,3′-f)thieno(3,2-b)thio- from 60% to 80%. Since the atmospheric moisture could influence the
amount of water in the reaction vessel and the quality of the surface
phene (C10-DNTT) (Figures S7, S8, Supporting Information).
functionalization, fine-tuning over the deposition factors was required
The traps in the SiO2 surface could be eliminated by the OTS subject to the relative humidity.
treatment and thereby the drain current (IDS) is significantly The AFM images were scanned by the Asylum MFP-3D system
increased, validating the critical role of surface functionaliza- in tapping mode and the contact angles were measured by the
tion in the OTFTs. It is worthwhile to mention that the organic drop shape analyzer (KRÜSS). The surface energy was calculated by
thin-film transistors fabricated from FDTS SAMs manifest Owen–Wendt–Rabel–Kaelble model. XPS results were taken by an
larger drain currents and threshold voltage shifts (Figure S9, X-ray photoelectron spectrometer (Escalab Xi+) and analyzed by the
software of Advantage.
Supporting Information), which is attributed to the accumula- Fabrication and Characterization of Organic Thin-Film Transistors: The
tion of holes in the conduction channel by SAMs with fluorine OTFT with staggered bottom gate architecture was constructed on the
groups.[20] SiO2/Si. Three interfaces were integrated into the fabrication of the
organic transistors, including non-treated, defective OTS (processed
at TD = 120 °C and PD = 0.2 bar) and defect-free OTS (processed at
TD = 160 °C and PD = 0.02 bar). Forty nanometers of DNTT/C10-DNTT
3. Conclusion (Luminescence Technology Corp.) were thermally evaporated as
the active layer with an evaporation rate of 0.3 Å s−1 and a substrate
In summary, the surface functionalization of FDTS is com- temperature of 60/80 °C. The top contact was realized by evaporating
prehensively studied by varying the vapor phase growing 30 nm Au on the organic layer through the shadow mask. The
condition. It is confirmed that a high deposition temperature evaporation rate was 0.3 Å s−1 while the base pressure was 9 × 10−7 mbar.
(TD ≥ 120 °C) is required to eliminate the defect on the surface Both thermal evaporations were carried out in the glove box. After
of the SAM-modified substrate. Meanwhile, the high vacuum fabrication, the active layers were scratched by needles to reduce the
fringe and gate leakage current. The electrical tests were performed by
degree (PD ≤ 0.02 bar) is essential to reduce the moisture and
a parameter analyzer (Keithley 4200). The transfer characteristics were
remove the aggregation defects. The successful deposition of measured at VD = −80 V and the µh was determined from the following
the FDTS layer on Si substrate is verified by XPS with a sur- equation:
face energy of 10.33 mJ m−2 and a thickness of 1.31 nm. It is
appealing that the surface functionalization could be scaled up µhC i W
IDS =
2 L G
(V − VTH )2 (6)
to 4-inch wafer scale. The generality of the growth condition
is validated by applying the frequently used SAMs, including
where the areal capacitance Ci is 11 nF cm−2 for 300 nm SiO2, W/L is 1.14
OTS and PTS. Finally, surface functionalization is employed in and VTH is the threshold voltage. In addition, the output curves were
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Adv Materials Inter - 2023 - Chen - Wafer‐Scale Highly Uniform Surface Functionalization from Vapor Phase and Applications

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Wafer-Scale, Highly Uniform Surface Functionalization from

Particularly, it is believed that surface

the solvents, etc.[28]

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