Cancel the control template for the tree to change the border. If you have Expression Blend, you can easily extract the default control template, and then you can just tickle the corresponding radius at the very top border.
MSDN, treeview:
<Style x:Key="{x:Type TreeView}" TargetType="TreeView">
<Setter Property="OverridesDefaultStyle" Value="True" />
<Setter Property="SnapsToDevicePixels" Value="True" />
<Setter Property="ScrollViewer.HorizontalScrollBarVisibility" Value="Auto"/>
<Setter Property="ScrollViewer.VerticalScrollBarVisibility" Value="Auto"/>
<Setter Property="Template">
<Setter.Value>
<ControlTemplate TargetType="TreeView">
<Border
Name="Border"
CornerRadius="1"
Background="{StaticResource WindowBackgroundBrush}"
BorderBrush="{StaticResource SolidBorderBrush}"
BorderThickness="1" >
<ScrollViewer
Focusable="False"
CanContentScroll="False"
Padding="4">
<ItemsPresenter/>
</ScrollViewer>
</Border>
</ControlTemplate>
</Setter.Value>
</Setter>
</Style>
, , , .