# Controlled Crystallinity of TiO2 Layers Grown by Atmospheric Pressure Spatial Atomic Layer Deposition and their Impact on Perovskite Solar Cell Efficiency

Authors: Eugen Zimmermann; Ka Kan Wong; Tobias Seewald; Julian Kalb; Jonathan Linke; Giso Hahn; Lukas Schmidt-Mende
Journal: International Journal of Photoenergy
 (2022)

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## Abstract

Atmospheric Pressure Spatial Atomic Layer Deposition (AP-SALD) is an upcoming deposition technique suitable for a variety of materials and combines the benefits of a regular atomic layer deposition with a significantly increased deposition rate at ambient conditions. In this work, amorphous and anatase TiO2 layers are fabricated by AP-SALD via systematic variation of process conditions such as temperature, reactant (H2O and O3), and posttreatment. The formed layers are characterized for their structural and optoelectronic properties and utilized as a hole-blocking layer in hybrid perovskite solar cells. It is found that TiO2 layers fabricated at elevated deposition temperatures possess strong anatase character but expose an unfavorable interface to the perovskite layer, promoting recombination and lowering the shunt resistance and open circuit voltage of the solar cells. Therefore, the interface is essential for efficient charge extraction, which can be significantly improved by controlling the process parameters.


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## Body

## 1. Introduction

TiO2 is an earth-abundant and very versatile material used in many optoelectronic and electronic applications like water splitting [1], gas sensing [2, 3], transistors [4–6], and solar cells. Its n-type character, an optical bandgap of about 3.0, 3.2, or 3.5 eV for rutile, anatase, and amorphous morphology, respectively, and its suitable energetic landscape have made it a commonly used electron selective layer in solar cells for almost 30 years [7–9]. During this time, many fabrication techniques for thin film and nanostructured layers have been developed, including spray pyrolysis [10–12], sputter deposition [13], electron-beam evaporation [14], chemical vapour deposition [15], sol-gel process [16–18], electrodeposition [19, 20], hydrothermal growth [21, 22], and atomic layer deposition (ALD) [23–26]. Thereby, ALD is of particular interest, as it allows the reproducible fabrication of pin-hole free layers of high quality on flat films and conformal coatings on nanostructures. Additionally, the resulting layer properties, like thickness and crystallinity, are precisely adjustable by the processing conditions such as temperature, pressure, purge, and exposure time as well as by the choice of precursor and reactant. Typically, TiCl4, titanium tetraisopropoxide (TTIP), and tetrakis dimethylamino titanium are used as precursors and H2O, H2O2, and O3 as reactant. Spatial atomic layer deposition at atmospheric pressure (AP-SALD) is the next evolutionary step of ALD and extends the precise thickness control of ALD by a fast vacuum free and upscalable deposition in ambient environment [27, 28].Here, we demonstrate the controlled fabrication of amorphous and anatase TiO2 by AP-SALD and relate the influence of processing parameters to structural, optical, and electronic properties and their implication on the performance of perovskite solar cells.


## 2. Methods

### 2.1. TiO2 Layer Preparation

TiO2 layers were fabricated on a homemade AP-SALD system with one precursor and one reactant line, and three curtain lines, each with an outlet area of 3.5 mm2. TTIP (>97%, Sigma Aldrich) was used as metal source precursor and H2O or O3 as reactant. In order to avoid condensation, the titanium precursor, transport tubes, and deposition head were preheated to 85°C. Bubble flow rate for N2 was set to 150 Nml/min for TTIP and 100 Nml/min for H2O. Flow rate of the N2 transport gas stream was set to 300 Nml/min in both cases, whereas the flow rate of the N2 curtain line was set to 600 Nml/min. O3 flow rate, with oxygen as transport gas, was manually adjusted in line with the H2O flow rate. Substrates were held on a heated stage by vacuum and passed the deposition head twice for one cycle. The distance between deposition head and substrate was adjusted to about 250 μm. For layer fabrication with an incorporated temperature gradient, the first layer was deposited at the initial temperature which then was smoothly increased/decreased until the final temperature was reached.Layers for Raman spectroscopy and profilometer measurements were fabricated on microscope glass slides. Layers for atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), spectroscopic ellipsometry (SE), X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS), and Kelvin probe (KP) were fabricated on polished silicon (111, n-type, Active Business Company GmbH) wafers, and for ultraviolet–visible spectroscopy (UV-Vis) and solar cells on tin-doped indium oxide (ITO, <15Ω/□, Luminescence Technology Corp.). Layers for Transmission Electron Microscopy (TEM) and selected area diffraction (SAD) were directly fabricated on 75 nm Si3N4 (S171-3, Agar Scientific) membranes. Sample thickness has been varied in terms of deposition cycles: 2000 cycles for Raman spectroscopy, 75 and 1000 cycles for UPS/XPS, 500 to 2000 cycles for thickness calibration by ellipsometry, 800 cycles for TEM and SAD, and 1000 cycles for all other measurements.Layers for XPS and UPS have been used as fabricated without cleaning or sputtering to exclude change in atomic composition and bindings.As reference, a~70 nm thick TiO2 layer was deposited by spin-casting a commercial sol-gel paste (Ti-Nanoxide BL/SC, Solaronix) and sintered at 450°C for 30 minutes.


### 2.2. Perovskite Solar Cell Preparation

The perovskite solar cells (MAPbI, CH3NH3PbI3) were fabricated via a two-step deposition method. All chemicals were used as purchased without further purification. ITO coated glass substrates were ultrasonically cleaned for 5 min in detergent, acetone, and isopropanol consecutively, followed by N2 drying. Subsequently, a TiO2 blocking layer was deposited on the substrates either by AP-SALD or via the sol-gel process as reference. In case of modification by [6,6]-phenyl-C61-butyric acid (PCBA, Solenne BV), the substrates were emerged into a PCBA bath (0.2 mM in chloroform) for 1 hour. They were then transferred to a glove-box where moisture and oxygen levels were kept below 5 ppm. PbI2 solution (1 M in anhydrous dimethylformamide) and substrates were preheated and maintained at 60°C before spin-coating. Hot PbI2 solution was spin-cast on the substrates at 5000 rpm for 15 s, which were then quickly transferred onto a hotplate at 70°C for drying. Subsequently, substrates were drop-coated with 6.54 w/v % methylammonium iodide (Solaronix) in anhydrous isopropanol for 20 s, spun at 4000 rpm for 20 s, and annealed at 100°C for 10 min. Spiro-OMeTAD (80 mg/ml, Merck) was spin-cast at 4000 rpm for 120 s, and WO3 (3 nm)/Ag (100 nm) were finally deposited on top by thermal evaporation.


## 2.1. TiO2 Layer Preparation

TiO2 layers were fabricated on a homemade AP-SALD system with one precursor and one reactant line, and three curtain lines, each with an outlet area of 3.5 mm2. TTIP (>97%, Sigma Aldrich) was used as metal source precursor and H2O or O3 as reactant. In order to avoid condensation, the titanium precursor, transport tubes, and deposition head were preheated to 85°C. Bubble flow rate for N2 was set to 150 Nml/min for TTIP and 100 Nml/min for H2O. Flow rate of the N2 transport gas stream was set to 300 Nml/min in both cases, whereas the flow rate of the N2 curtain line was set to 600 Nml/min. O3 flow rate, with oxygen as transport gas, was manually adjusted in line with the H2O flow rate. Substrates were held on a heated stage by vacuum and passed the deposition head twice for one cycle. The distance between deposition head and substrate was adjusted to about 250 μm. For layer fabrication with an incorporated temperature gradient, the first layer was deposited at the initial temperature which then was smoothly increased/decreased until the final temperature was reached.Layers for Raman spectroscopy and profilometer measurements were fabricated on microscope glass slides. Layers for atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), spectroscopic ellipsometry (SE), X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS), and Kelvin probe (KP) were fabricated on polished silicon (111, n-type, Active Business Company GmbH) wafers, and for ultraviolet–visible spectroscopy (UV-Vis) and solar cells on tin-doped indium oxide (ITO, <15Ω/□, Luminescence Technology Corp.). Layers for Transmission Electron Microscopy (TEM) and selected area diffraction (SAD) were directly fabricated on 75 nm Si3N4 (S171-3, Agar Scientific) membranes. Sample thickness has been varied in terms of deposition cycles: 2000 cycles for Raman spectroscopy, 75 and 1000 cycles for UPS/XPS, 500 to 2000 cycles for thickness calibration by ellipsometry, 800 cycles for TEM and SAD, and 1000 cycles for all other measurements.Layers for XPS and UPS have been used as fabricated without cleaning or sputtering to exclude change in atomic composition and bindings.As reference, a~70 nm thick TiO2 layer was deposited by spin-casting a commercial sol-gel paste (Ti-Nanoxide BL/SC, Solaronix) and sintered at 450°C for 30 minutes.


## 2.2. Perovskite Solar Cell Preparation

The perovskite solar cells (MAPbI, CH3NH3PbI3) were fabricated via a two-step deposition method. All chemicals were used as purchased without further purification. ITO coated glass substrates were ultrasonically cleaned for 5 min in detergent, acetone, and isopropanol consecutively, followed by N2 drying. Subsequently, a TiO2 blocking layer was deposited on the substrates either by AP-SALD or via the sol-gel process as reference. In case of modification by [6,6]-phenyl-C61-butyric acid (PCBA, Solenne BV), the substrates were emerged into a PCBA bath (0.2 mM in chloroform) for 1 hour. They were then transferred to a glove-box where moisture and oxygen levels were kept below 5 ppm. PbI2 solution (1 M in anhydrous dimethylformamide) and substrates were preheated and maintained at 60°C before spin-coating. Hot PbI2 solution was spin-cast on the substrates at 5000 rpm for 15 s, which were then quickly transferred onto a hotplate at 70°C for drying. Subsequently, substrates were drop-coated with 6.54 w/v % methylammonium iodide (Solaronix) in anhydrous isopropanol for 20 s, spun at 4000 rpm for 20 s, and annealed at 100°C for 10 min. Spiro-OMeTAD (80 mg/ml, Merck) was spin-cast at 4000 rpm for 120 s, and WO3 (3 nm)/Ag (100 nm) were finally deposited on top by thermal evaporation.


## 3. Results

To aim for high quality TiO2 thin films and their desired application in solar cells, we comprehensively investigated the role of varying deposition parameters on layer formation, crystallinity, and interfacial effects. Therefore, we systematically varied the deposition temperature and the reactant (H2O and O3) during the AP-SALD process and analyzed the resulting structural and optoelectronic properties, as well as basic solar cell characteristics.


### 3.1. Structural Analysis

The layers for structural analysis were fabricated at sample temperatures between 100 and 400°C with a fixed number of cycles underneath the deposition head. The resulting thickness was determined by profilometer measurements and spectroscopic ellipsometry, yielding a growth per cycle (GPC) rate of about 0.7-1 Å/cycle for H2O and slightly lower for O3 as reactant (see Table 1 and Figure S1 in SI).Table 1
Summary of measured and modeled structural and optical properties.
Temperature (°C)AFMSE modelUV-VisKPUPSRMS (nm)Roughness (nm)Thickness (nm)GPC (nm/cycle)MSEn (530)Egap (eV)WF (eV)WF (eV)VBM (eV)H2O1001.21.789.90.090.72.073.53-4.58-4.54-7.411500.91.982.40.080.62.193.53-4.58-4.72-7.512001.12.984.40.080.62.373.51-4.65-4.54-7.2625010.07.51050.113.82.543.49-4.65-4.74-7.463008.511.9114.50.113.92.533.45-4.70-4.73-7.4635011.211.6111.70.114.52.543.36-4.70-4.76-7.55O3100—289.50.091.22.073.49-4.59-4.73-7.591500.81.775.60.081.12.213.50-4.47-4.72-7.522001.01.653.30.050.72.403.45-4.48-4.71-7.402502.31.959.40.061.62.563.34-4.70-4.70-7.3830012.63.189.40.096.02.553.43-4.62-4.77-7.5435013.95.186.10.096.22.573.30-4.67-4.77-7.46XPS measurements of thin (75 cycles~6 nm) and thick (1000 cycles~80 nm) layers confirm that samples at all temperatures consist of TiO2 with comparable carbon contamination of the surface determined by the C 1s peak at 285 eV. The major titanium peak Ti 2p3/2 is detected at a binding energy of 458.8 eV and can be assigned to an oxidation state of Ti4+, whereas the corresponding O 1s signal is in accordance shifted to 530.3 eV (see Figures 1 and 2 as well as Figure S2 to S4 in the SI) [29–31]. Deconvolution of the O 1s peak into an Ti4+ (530.4 eV) and an Ti3+ (532 eV) contribution, the Ti3+ content is notably decreasing with increasing temperature, indicating a reduction of defects for both reactants [32, 33].Figure 1
XPS overview scans of TiO2 with (a) H2O and (b) O3 as reactant at varying deposition temperatures and 1000 deposition cycles.
(a)(b)Figure 2
XPS detailed scans of Ti 2p, O 1s, and C 1s of TiO2 samples with (a, c, e) H2O and (b, d, f) O3 as reactant at varying deposition temperatures and 1000 deposition cycles.
(a)(b)(c)(d)(e)(f)SEM images of investigated layers for sample temperatures between 100 and 350°C are shown in Figure3 (more details in Figure S5 to S16 in the SI). For H2O as reactant, deposited layers start to crystallize in the anatase phase at sample temperatures of 200°C. Thereby, an amorphous layer is formed prior to nucleation of small anatase crystallites, which is also evident from the transmission electron microscopy and the selected area electron diffraction of the corresponding regions shown in Figure 4. As temperature increases above 250°C, the crystallization process is strongly enhanced and crystallites with preferential growth orientation are formed. First, the crystal growth is leading to flat terrace-like grains with sizes of 200 to 300 nm. For further increased temperatures, the crystal shape is changing to a plate-like structure with dimensions of about 100 nm. A similar crystallization process was described for TiCl4 as Ti-precursor in regular ALD systems [23, 34, 35] and recently was also described for TTIP and H2O in another AP-SALD system [36], though with a slightly different temperature onset for crystallization of anatase layers.Figure 3
SEM images of TiO2 layers on Si fabricated between 100°C and 350°C with H2O (a) and O3 (b) as reactant and 1000 deposition cycles.
(a)(b)Figure 4
TEM and SAD images of TiO2 layers fabricated with H2O as reactant at deposition temperatures of (a) 100, (b) 200, and (c) 300°C and 800 deposition cycles.
(a)(b)(c)With O3 as reactant, the crystallization process starts at higher temperatures and leads to significantly larger grain sizes of more than 1 μm. As in case of H2O, the grain-size decreases with increasing temperatures, but the terrace-like facets remain more discernable. The structural change combined with the temperature-dependent variation in growth rate suggest a transition from a space-limited (due to a small amount of nucleation sites) to a general crystal growth with increasing temperature, superimposed by Ostwald ripening at intermediate and decomposition of the precursor at elevated temperatures [34, 36, 37]. Furthermore, for both reactants this transition is associated with a change in surface roughness, which is increasing from about 1 to 10 nm root mean square (RMS). This is evident from AFM (see Figure S17 in the SI) measurements and consistent with fit parameters extracted from the utilized SE model (compare Table 1). The different results between H2O and O3 in terms of morphology and growth rate are attributed to a different chemisorption of the incoming TTIP precursor and the respective surface reaction mechanism, as well as the resulting surface area available for the process [38–41].For both reactants, the change from amorphous to the anatase structure is verified by Raman spectra, as seen in Figure5. Thereby, for deposition temperatures below 250 and 300°C for H2O and O3, respectively, layers show mainly amorphous character. For higher temperatures, detected peak positions correspond to literature values of anatase at 144, 196, 397, 513/519, and 639 cm−1, whereas rutile signals at 143, 447, 612, or 826 cm−1 are not observable [42, 43]. The significant increase in Raman intensity with higher temperature is attributed to an increasing crystallinity as indicated from SEM images in Figure 3. This is also consistent with EDX measurements showing a raise in the atomic percentage of titanium and oxygen relative to the silicon substrate for increasing temperatures (see Figure S18 and Table S1 in the SI) due to an increase in layer density. Thereby, the atomic percentage of Ti is increasing linearly from 4.5 to 10% for H2O starting at deposition temperatures of 100°C, whereas for O3 the values only start to rise above 200°C. This goes along with a decrease of the O : Ti ratio from about 3.5 to 2.8, assuming the contribution by a native SiO2 layer on the Si substrate to be insignificant.Figure 5
Raman spectra of fabricated TiO2 layers for (a) H2O and (b) O3 as reactant and 2000 deposition cycles. Layers are analyzed for anatase (A) and rutile (R) crystal structure. Distinct signals for anatase are observed for temperatures of at least 250°C and 300°C for H2O and O3 as reactant, respectively.
(a)(b)We note that intensities in Raman and EDX are sensitive to variations in layer density and thickness. However, the relatively small variation in layer thickness does not explain the significant increase of the Raman intensity towards higher process temperatures. In addition, XPS, which is not thickness-dependent, also shows increased signal intensities while the C 1s peak is not systematically affected (see Figure2). Hence, the change of atomic percentage is attributed to an increased packing density due to enhanced crystallinity. Table 1 is summarizing relevant properties extracted from structural and optoelectronic measurement techniques.


### 3.2. Optical and Electronic Analysis

Optical and electronic properties were investigated by UPS, KP, UV-Vis, SE, and in terms of solar cells. The corresponding measurements are shown in FiguresS19 and S20 (UPS), Figure S21 (UV-Vis), and Figures S22 and S23 (SE) in the SI.From UPS and KP measurements, the work function (WF) and valence band maximum (VBM) were determined at energies of about −4.6 eV and −7.5 eV, respectively. In combination with the optical bandgap determined from UV-Vis, the conduction band minimum of fabricated TiO2 layers is located at an energy of about −3.9 to −4.0 eV and therefore the Fermi level is steadily 0.7 eV below the conduction band. The corresponding measurements are presented in Table 1 and Figure S24 in the SI.Meanwhile, the optical bandgap and the extinction coefficient are consistently shifting to lower energies with increasing deposition temperatures as expected for an increasing crystallinity [8], and the change in crystallinity results in a significant increase in refractive index from about 2.07 to 2.54 and 2.57 at 530 nm for H2O and O3, respectively. This has to be considered for light propagation and standing wave formation within solar cell devices, which can modulate the resulting short circuit current density (JSC) [44, 45].The influence of varying TiO2 properties on solar cell characteristics was exemplarily inspected on perovskite-based solar cells (MAPbI3, 2-step process) utilizing AP-SALD layers with the most promising conditions or variations. Fabricated devices have been compared to a commercial sol-gel reference without further optimization (see Figure 6), yielding flat, at about 70 nm thick compact layers with a surface roughness and morphology comparable to amorphous AP-SALD layers fabricated at temperatures of 200°C and below. More detailed device characteristics of fabricated solar cells are shown in Figures S25 to S30 in the SI.Figure 6
Thickness dependent solar cell characteristics for PCBA modified (left) and unmodified (right) SALD layers fabricated at 200°C. Reference layer were fabricated with a commercial sol-gel. Solar cells have been measured in forward (open circle), reverse (x), and under steady state conditions (filled circle). The different panels show theJSC, VOC, Fill factor (FF), Rseries, RSh, and the power conversion efficiency, respectively.Compared to the reference sample prepared with commercial TiO2 paste, the series resistance is higher and shunt resistance is lower in AP-SALD-based solar cells, which is directly reflected in a decreased fill factor. The slightly higher series resistance is attributed to the complete absence of unintentional doping and a more stoichiometric TiO2 crystal formation with less oxygen vacancies during deposition. These vacancies are known to be responsible for the intrinsic conductivity of TiO2 [46]. The decreased shunt resistance, on the other hand, is attributed to the TiO2 interface of as-processed layers to the perovskite. The absence of dopants and impurities within the bulk and at the surface of the fabricated layers presumably leads to an unfavorable energy landscape for electron extraction, which was already observed for TiO2 and other metal oxides [47–49]. Thus, a surface passivation by PCBA strongly enhanced open circuit voltage (VOC) and fill factor of fabricated devices.However, this impact of the interface is strongly interfering with a direct association of layer properties to device characteristics. Thus, in spite of significant changes in layer properties like layer thickness, morphology, crystallinity, and stoichiometry, clear systematic dependencies of device characteristics were largely superimposed and are mainly within our given uncertainty of device reproducibility.Common strategies for interface passivation are the application of very thin organic [50–52] or inorganic [53, 54] interface layers which are improving charge extraction and avoiding recombination. Also, ultrathin ALD layers of amorphous TiO2 have been shown to act as suitable passivation layer [55].Integrating this approach into the AP-SALD deposition by a continuous gradual change of temperature allows for an uninterrupted fabrication process of the TiO2, reducing complexity and avoiding a possible contamination of the surface between fabrication steps. Therefore, we investigated the influence of temperature gradients during deposition and compared them to layers deposited at fixed temperatures. For layers fabricated with a temperature gradient from 300 to 100°C we find a significant improvement in all device characteristics (see Figure 7) and attribute this to the formation of a core-shell structure with an amorphous layer covering a crystalline anatase film. This combines the good series resistance of the crystalline phase with an improved interface avoiding recombination [56].Figure 7
Steady state device characteristics of solar cells fabricated on TiO2 deposited with 1000 cycles at 100°C, 300°C, and with a gradient from 300°C to 100°C (the latter for two different batches of devices with high reproducibility). Sol-gel-based TiO2 solar cell as reference. All devices without PCBA modification: (a) maximum power-point (MPP), (b) VOC, and c) JSC tracking over time.
(a)(b)(c)


## 3.1. Structural Analysis

The layers for structural analysis were fabricated at sample temperatures between 100 and 400°C with a fixed number of cycles underneath the deposition head. The resulting thickness was determined by profilometer measurements and spectroscopic ellipsometry, yielding a growth per cycle (GPC) rate of about 0.7-1 Å/cycle for H2O and slightly lower for O3 as reactant (see Table 1 and Figure S1 in SI).Table 1
Summary of measured and modeled structural and optical properties.
Temperature (°C)AFMSE modelUV-VisKPUPSRMS (nm)Roughness (nm)Thickness (nm)GPC (nm/cycle)MSEn (530)Egap (eV)WF (eV)WF (eV)VBM (eV)H2O1001.21.789.90.090.72.073.53-4.58-4.54-7.411500.91.982.40.080.62.193.53-4.58-4.72-7.512001.12.984.40.080.62.373.51-4.65-4.54-7.2625010.07.51050.113.82.543.49-4.65-4.74-7.463008.511.9114.50.113.92.533.45-4.70-4.73-7.4635011.211.6111.70.114.52.543.36-4.70-4.76-7.55O3100—289.50.091.22.073.49-4.59-4.73-7.591500.81.775.60.081.12.213.50-4.47-4.72-7.522001.01.653.30.050.72.403.45-4.48-4.71-7.402502.31.959.40.061.62.563.34-4.70-4.70-7.3830012.63.189.40.096.02.553.43-4.62-4.77-7.5435013.95.186.10.096.22.573.30-4.67-4.77-7.46XPS measurements of thin (75 cycles~6 nm) and thick (1000 cycles~80 nm) layers confirm that samples at all temperatures consist of TiO2 with comparable carbon contamination of the surface determined by the C 1s peak at 285 eV. The major titanium peak Ti 2p3/2 is detected at a binding energy of 458.8 eV and can be assigned to an oxidation state of Ti4+, whereas the corresponding O 1s signal is in accordance shifted to 530.3 eV (see Figures 1 and 2 as well as Figure S2 to S4 in the SI) [29–31]. Deconvolution of the O 1s peak into an Ti4+ (530.4 eV) and an Ti3+ (532 eV) contribution, the Ti3+ content is notably decreasing with increasing temperature, indicating a reduction of defects for both reactants [32, 33].Figure 1
XPS overview scans of TiO2 with (a) H2O and (b) O3 as reactant at varying deposition temperatures and 1000 deposition cycles.
(a)(b)Figure 2
XPS detailed scans of Ti 2p, O 1s, and C 1s of TiO2 samples with (a, c, e) H2O and (b, d, f) O3 as reactant at varying deposition temperatures and 1000 deposition cycles.
(a)(b)(c)(d)(e)(f)SEM images of investigated layers for sample temperatures between 100 and 350°C are shown in Figure3 (more details in Figure S5 to S16 in the SI). For H2O as reactant, deposited layers start to crystallize in the anatase phase at sample temperatures of 200°C. Thereby, an amorphous layer is formed prior to nucleation of small anatase crystallites, which is also evident from the transmission electron microscopy and the selected area electron diffraction of the corresponding regions shown in Figure 4. As temperature increases above 250°C, the crystallization process is strongly enhanced and crystallites with preferential growth orientation are formed. First, the crystal growth is leading to flat terrace-like grains with sizes of 200 to 300 nm. For further increased temperatures, the crystal shape is changing to a plate-like structure with dimensions of about 100 nm. A similar crystallization process was described for TiCl4 as Ti-precursor in regular ALD systems [23, 34, 35] and recently was also described for TTIP and H2O in another AP-SALD system [36], though with a slightly different temperature onset for crystallization of anatase layers.Figure 3
SEM images of TiO2 layers on Si fabricated between 100°C and 350°C with H2O (a) and O3 (b) as reactant and 1000 deposition cycles.
(a)(b)Figure 4
TEM and SAD images of TiO2 layers fabricated with H2O as reactant at deposition temperatures of (a) 100, (b) 200, and (c) 300°C and 800 deposition cycles.
(a)(b)(c)With O3 as reactant, the crystallization process starts at higher temperatures and leads to significantly larger grain sizes of more than 1 μm. As in case of H2O, the grain-size decreases with increasing temperatures, but the terrace-like facets remain more discernable. The structural change combined with the temperature-dependent variation in growth rate suggest a transition from a space-limited (due to a small amount of nucleation sites) to a general crystal growth with increasing temperature, superimposed by Ostwald ripening at intermediate and decomposition of the precursor at elevated temperatures [34, 36, 37]. Furthermore, for both reactants this transition is associated with a change in surface roughness, which is increasing from about 1 to 10 nm root mean square (RMS). This is evident from AFM (see Figure S17 in the SI) measurements and consistent with fit parameters extracted from the utilized SE model (compare Table 1). The different results between H2O and O3 in terms of morphology and growth rate are attributed to a different chemisorption of the incoming TTIP precursor and the respective surface reaction mechanism, as well as the resulting surface area available for the process [38–41].For both reactants, the change from amorphous to the anatase structure is verified by Raman spectra, as seen in Figure5. Thereby, for deposition temperatures below 250 and 300°C for H2O and O3, respectively, layers show mainly amorphous character. For higher temperatures, detected peak positions correspond to literature values of anatase at 144, 196, 397, 513/519, and 639 cm−1, whereas rutile signals at 143, 447, 612, or 826 cm−1 are not observable [42, 43]. The significant increase in Raman intensity with higher temperature is attributed to an increasing crystallinity as indicated from SEM images in Figure 3. This is also consistent with EDX measurements showing a raise in the atomic percentage of titanium and oxygen relative to the silicon substrate for increasing temperatures (see Figure S18 and Table S1 in the SI) due to an increase in layer density. Thereby, the atomic percentage of Ti is increasing linearly from 4.5 to 10% for H2O starting at deposition temperatures of 100°C, whereas for O3 the values only start to rise above 200°C. This goes along with a decrease of the O : Ti ratio from about 3.5 to 2.8, assuming the contribution by a native SiO2 layer on the Si substrate to be insignificant.Figure 5
Raman spectra of fabricated TiO2 layers for (a) H2O and (b) O3 as reactant and 2000 deposition cycles. Layers are analyzed for anatase (A) and rutile (R) crystal structure. Distinct signals for anatase are observed for temperatures of at least 250°C and 300°C for H2O and O3 as reactant, respectively.
(a)(b)We note that intensities in Raman and EDX are sensitive to variations in layer density and thickness. However, the relatively small variation in layer thickness does not explain the significant increase of the Raman intensity towards higher process temperatures. In addition, XPS, which is not thickness-dependent, also shows increased signal intensities while the C 1s peak is not systematically affected (see Figure2). Hence, the change of atomic percentage is attributed to an increased packing density due to enhanced crystallinity. Table 1 is summarizing relevant properties extracted from structural and optoelectronic measurement techniques.


## 3.2. Optical and Electronic Analysis

Optical and electronic properties were investigated by UPS, KP, UV-Vis, SE, and in terms of solar cells. The corresponding measurements are shown in FiguresS19 and S20 (UPS), Figure S21 (UV-Vis), and Figures S22 and S23 (SE) in the SI.From UPS and KP measurements, the work function (WF) and valence band maximum (VBM) were determined at energies of about −4.6 eV and −7.5 eV, respectively. In combination with the optical bandgap determined from UV-Vis, the conduction band minimum of fabricated TiO2 layers is located at an energy of about −3.9 to −4.0 eV and therefore the Fermi level is steadily 0.7 eV below the conduction band. The corresponding measurements are presented in Table 1 and Figure S24 in the SI.Meanwhile, the optical bandgap and the extinction coefficient are consistently shifting to lower energies with increasing deposition temperatures as expected for an increasing crystallinity [8], and the change in crystallinity results in a significant increase in refractive index from about 2.07 to 2.54 and 2.57 at 530 nm for H2O and O3, respectively. This has to be considered for light propagation and standing wave formation within solar cell devices, which can modulate the resulting short circuit current density (JSC) [44, 45].The influence of varying TiO2 properties on solar cell characteristics was exemplarily inspected on perovskite-based solar cells (MAPbI3, 2-step process) utilizing AP-SALD layers with the most promising conditions or variations. Fabricated devices have been compared to a commercial sol-gel reference without further optimization (see Figure 6), yielding flat, at about 70 nm thick compact layers with a surface roughness and morphology comparable to amorphous AP-SALD layers fabricated at temperatures of 200°C and below. More detailed device characteristics of fabricated solar cells are shown in Figures S25 to S30 in the SI.Figure 6
Thickness dependent solar cell characteristics for PCBA modified (left) and unmodified (right) SALD layers fabricated at 200°C. Reference layer were fabricated with a commercial sol-gel. Solar cells have been measured in forward (open circle), reverse (x), and under steady state conditions (filled circle). The different panels show theJSC, VOC, Fill factor (FF), Rseries, RSh, and the power conversion efficiency, respectively.Compared to the reference sample prepared with commercial TiO2 paste, the series resistance is higher and shunt resistance is lower in AP-SALD-based solar cells, which is directly reflected in a decreased fill factor. The slightly higher series resistance is attributed to the complete absence of unintentional doping and a more stoichiometric TiO2 crystal formation with less oxygen vacancies during deposition. These vacancies are known to be responsible for the intrinsic conductivity of TiO2 [46]. The decreased shunt resistance, on the other hand, is attributed to the TiO2 interface of as-processed layers to the perovskite. The absence of dopants and impurities within the bulk and at the surface of the fabricated layers presumably leads to an unfavorable energy landscape for electron extraction, which was already observed for TiO2 and other metal oxides [47–49]. Thus, a surface passivation by PCBA strongly enhanced open circuit voltage (VOC) and fill factor of fabricated devices.However, this impact of the interface is strongly interfering with a direct association of layer properties to device characteristics. Thus, in spite of significant changes in layer properties like layer thickness, morphology, crystallinity, and stoichiometry, clear systematic dependencies of device characteristics were largely superimposed and are mainly within our given uncertainty of device reproducibility.Common strategies for interface passivation are the application of very thin organic [50–52] or inorganic [53, 54] interface layers which are improving charge extraction and avoiding recombination. Also, ultrathin ALD layers of amorphous TiO2 have been shown to act as suitable passivation layer [55].Integrating this approach into the AP-SALD deposition by a continuous gradual change of temperature allows for an uninterrupted fabrication process of the TiO2, reducing complexity and avoiding a possible contamination of the surface between fabrication steps. Therefore, we investigated the influence of temperature gradients during deposition and compared them to layers deposited at fixed temperatures. For layers fabricated with a temperature gradient from 300 to 100°C we find a significant improvement in all device characteristics (see Figure 7) and attribute this to the formation of a core-shell structure with an amorphous layer covering a crystalline anatase film. This combines the good series resistance of the crystalline phase with an improved interface avoiding recombination [56].Figure 7
Steady state device characteristics of solar cells fabricated on TiO2 deposited with 1000 cycles at 100°C, 300°C, and with a gradient from 300°C to 100°C (the latter for two different batches of devices with high reproducibility). Sol-gel-based TiO2 solar cell as reference. All devices without PCBA modification: (a) maximum power-point (MPP), (b) VOC, and c) JSC tracking over time.
(a)(b)(c)


## 4. Conclusion

The analysis of structural and optoelectronical characterization methods shows a significant influence of temperature and the chosen reactant on crystallinity and grain size of deposited AP-SALD layers. Thereby, low deposition temperatures result in smooth amorphous TiO2 films, while elevated temperatures lead to polycrystalline anatase layers. With increasing deposition temperature, the preferential crystal growth is increasing the resulting surface area and roughness. Simultaneously, the improving crystallinity leads to a higher refractive index and lower optical band gap, though the energy levels of the layer are only slightly altered. In fabricated perovskite-based solar cells, the impact of an unfavorable interface restricts a clear association of TiO2 layer to specific changes in device characteristics and highlights once again the necessity of adequate interface engineering. Thus, a promising approach for gradual core-shell structures was demonstrated, leading to an amorphous passivation layer on top of highly crystalline anatase TiO2 for improved solar cells.



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